AU2015200758A1 - Carbohydrate binders and materials made therewith - Google Patents

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 contact 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.

Description

CARBOHYDRATE BINDERS AND MERMALS MADE THEREWITH CROSS-REFERENCE TO RELATED APPLICATION S This app cation claims the benefit of Un cited States provisional application 6 1/332,452, filed 7 May 2010, which is incorporated by reference herein. TECHNICAL FIELD [001] This closure relates to a under fmulation and materils mad thereit compiling a carbohydra-baned binder andaethod for preparing he same. In particular a binder comprinWg te reaction products of a carbohy t and a nucloplle and materials made thereith if describe BACKGROUND [002] Biders are usefibc ti fbratng aicles because they are capable of consolidating not or loosely assembled maten. Foar example, binders enable tw or nore surface to become united, In particular, binders may be used to produce products comprising consolidated fibers. Thermosetting binders may be characterized by being transformed into insoluble and infusible materials by means of either heat or catalytic action. Examples of a thermnostring binder include a variety of phenol-aidehyde unrea-akdehyd, melamine-aldehyde, and other condensation-polymerization materials ke furane and polyurethaneresis Bider composiions contaning pheno-albde resorcinol ldbyde, phenoalhyd rapheno/mniumine/aldehydeanhe like are used for the bonding of bersextis plastic bbers,an any other materials. [031 The ineral ooland iber boa indtrie hav historiayusedaphenol foaldehyde binder to bnd fiber Pheol formaldehyde yp binders provide suitable properties to the finaproduct however, environmental consideration have motiaed the devlopmentof alternative binder. One such alernatvbre iaearbohyate basedider deed om reactinga caohydrate and a mutiprotic acddfor emple, 1 Publshed ApplicationNo.200/002723 and Published PCTApplation W020091923 Another alternative binders the esterificato pr-ducts ofreacting agp carboxylic aid and apoyo ampl SPblsed ApplictionN 200/0202224 Because these binda donot utize formaldehyde as eageng they have been colleively referred 1o as formaldehyde-free binders. [004] One area of current development is to find a replacement for the phenol formaldehyde type binders across the entire range of products in the building and automotive sector (eg fiberglass insulation. particle boards, office panels, and acoustical sound insulation), in particular, the previously developed formaldehyde-free binders may not possess all of the desired properties for all the products in this sector. For exanle, acrylic acid and poly(vinylaleohol) based binders have shown promising performance characteristics. However, these are relatively more expensive than phenol formaldehyde hinders, arc derived essentially from petroleum-based resources, and have a tendency to exhibit lower reaction rates compared to the phenol formaldehyde based binder compositions (requiring either prolonged cure toes or increased cure temperatures Carbohydrate-based binder compositions are made of relatively inexpensive precursors and are derived mainly from renewable resources; however, these binders may also require reaction conditions for curing that are substantially different from those conditions under which the traditional phenol formaldehyde binder system cured. As such, facile replacement of phenol formaldehyde type binders with an existing alternative has not been readily achieve. SUMMARY [0051 According to the present disclosure, a carbohydrate based binder is described. The binder composition has properties that markc it useful for a variety of applications; particularly, the binder may be used to bind loosely assembled matter such as fibers, 1006} in illustrative embodiments, the present disclosure relates to a binder comprising a polymeric product of a carbohydrate reactant and a nucleophile. In one embodiment, the carbohydrate reactant is a polysaccharide. in one embodiment, the carbohydrate reactant is a monosaccharide or a disaccharide. In another embodiment, the carbohydrate is a monosaccharide in its aldose or ketosc form. in another embodiment, the carbohydrate reactant is selected from the group consisting of dextrose, ylose, fructose, dihydroxyacetone, and mixtures thereof, In another embodiment, the polymeric product is a thermoses polymeric product. [0071 In illustrative embodiments, the nucleophile is a di-functional In another embodiment, the nueleophile is R 1

-Q-R

2 , wherein Q is alkyl, cycloalkyl, heteroalkyl, or cycloheeroaikyl, each of which is optionally substituted having a nucleophulic moiety and a stabilization moiety, R 1 is 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, and an alkoxide, and R2 is selected from the group consisting of an amine, an amide, an imin, an imide, a nirro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulphono, a suipho. a sulfinyl, and a suifhydryl (thiol) in one ernbodhnent, the nucleophile includes an amine functional group. [008] hn illustrative embodiments, the mole ratio of the carbohydrate reactant to the nucleophile is in the range of about 1:1 to about 30:1, In another embodiment, the mole ratio of the carbohydrate reactant to the nucleophile is in the range of about 2:1 to about 10:1. Tn another emboditment, an aqueous extract of the polymearic product has a PH in the range of about 5 to about 9, it another embodiment, an aqueous extract of the polymeric product is essentially colorless. In yet another embodiment, the polymeric product is phenol-free and/or formaldehyde-free. In another embodiment, an aqueouis extract of the polymeric product is capable of reducing Benedict's reagent. in another ebodimnent, the polymeric product absorbs light between 400 and 500 n, for example, in one embodiment, at 420 nm l0091 in an illustrative embodiment a method of making a collection of mater bound with a polymeric binder comprises preparing a solution containing reactants for producing the polymeric binder and a solvent, wherein the reactats include a carbohydrate reactant and a nucleophile; disposing the solution onto the collection of matter; volatilizing the solvent to form an uncured prooct, and subjecting the uncured product to conditions that cause the carbohydrate reactant and the nucieophule to polymerize to form the polymeric binder. In one embodiment, the collection of matter comprises fibers selected from the group consisting of mineral fibers (slag wool fibers, rock wool fibers, or glass fibers), aranid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, and cellulosic fibers. in another embodiment the collection of matter comprises particulates 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 the range from about 70% to about 99% by weight. In another embodiment, the collection of matter comprises celkIlosic fibers. For example, the cellulosic fibers may be wood shavings, sawdust, wood pulp, or ground wood, Ii yet another embodiment, the cellulosic fibers may be other natural fibers such as jute, flax, hemp, or straw. [0101 In illustrative embodiments, the method of making a collection of matter bound with a polymeric binder further includes preparing a solution by adding an amount of a carbohydrate reactant and an amount of a nueleophile so that the molar ratio is in the range of about 2:1 to about 10:1, respectively. in one embodiment, preparing the solution includes adding the carbohydrate reactant and the nucleophite to an aqueous solution, in another embodiment preparing the solution includes adjusting the pH of the solution to within the range of about X to about 13, for example, in one embodiment, the range of about 8 to about 12. 101 1] In illustrative embodiments, the present disclosure relates to a composition comprising a collection of matter and a binder; the binder comprising the polymeric products of a reaction between a carbohydrate reactant and a nucleophile, the polymeric products being substantially water insoluble, in one enbodiment, the collection of matter includes mineral fibers (slag wool fibers, rock wool fibers, or glass fibers , aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyiride fibers, polyester fibers, rayon fibers, and cellulosic fibers For example, cellulosic fibers include wood shavings, sawdust, wood pulp, and/or ground wood, in one embodiment, the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the nucleophile is selected from the group consisting of a diamrine, trianmine, tetramin, and pentamine, in one embodiment, the nucleophile is R1-Q-R2, wherein Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteralkyl, each of which is optionally substituted, RI is a nucleophilic moiety, and R 2 is a stabilizattion moiety. In one embodiment, Rj is selected front the group cosisting anin an azide., cyanate, isocyanate, a .OL a di de a tocyan a halogen, a haloformyl, a carboxyl a carboxNylate, a hydroxyl, and an alkoxide, in another embodiment, R2 is selected from the group consisting of an amine, an anmide, an itnine, an imide, a nitro, a nitrate, a

-.

pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a suiphono, a sulpho, a sulinyl, and a sulfhydryl (thiol). [012) In another embodiment, the composition further comprises a silicon-containi compound, in one embodiment the silicon-containing compound is a functionalized silylether or a functionalized alkylsilylether, such as for example, an amnino-functionalized alkylsilylether, For example, in one embodiment, the silicon-containing compound may be ganmma aminopropyltrietboxysilan, gamnma-glycidoxypropyltrimethoxysilanc, or amninoethyianminopropyltrimethoxysijane, or a mixture thereof. In another embodiment, the silicon containing compound may be an aminofonctional oligomeric siloxane. In another embodiment, the composition comprises a corrosion inhibitor selected from the group consisting of dedusting oil, mona mmnoniumi phosphate, sodium metasilicate pentahydrate, melamine, tin(U) oxalate, and a mnethyihydrogen silicone fluid emulsion. BRIEF DESCRIPTION OF 'HE DRATWNGS [013] Fig. 1 shows a schematic of a Maiilard reaction, which culminates in the pro tionT of Jemelanoi dins. [0141 Fig. 2 shows a schematic of a representative Amadori rearrangemenm. [015] Fig. 3 shows the cure temperature profile (Y-axis in "C) of the center of a fiberglass mat sample for different binders during a heart molding cycle (X-axis in minutes of mold tine) using a mold press with a temperature controlled platen at 204 0 C Binder I (+) is a phenol formaldehyde binder (Comparative Example 2); Binder 2 (.)is a carbohydrate - inorganic acid binder (Comparative Example 3); and Binder 3 (X) is a dextrose -ammonia hexamethyene diamine (HMDA) binder (Example 5). DETA TU DESCRIPTION [01 6} While the invention is susceptible to various modification and alterative forms, specific embodiments will herein be described in detail. It should he understood, however, that there is no intent to limit the invention to the particular fonns described, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within dhe spirit and scope of the invention. [017 The present disclosure relates to a binder composition having unexpected utility in consolidating non- or loosei-assembled mater. The binder composition represents an unexpected advancement in the current state of technology in the area of binder compositions. Specifcally, the binder offers improvements in performance awad provides for more simplified and advantageous manufacturing methodologies, while maintaining the environmentally sound advantages that are characteristic of a carbohydrate based binder system, 10181 As used herein, tie term binder solution is the solution of chemicals which 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 composition of the uncured binder is referred to as an uncured binder composition. An uncured binder is a substantialy dehydrated mixture of chemicals which can be cured to form a cured binder, Substanilly dehydrated means that the solvent (typicaly water or a mixture there) used to make the binder solution is vaporized to the extent that the viscosiy of the remaining material (comprising the binder reactants and solvent) is sufficiently high to create chesion bet the elasenbed nrtterthusthe remnning materials an uncured binder I one embodiment, the solvent is less than 65% cube total weight of the remainin material in another embodiment, a substantially dehydrated binder has a moisture content between about 5% and about 65% water by weight of total binder. In another embodiment, the solvent may be less than 50% of the total weight of the remaining material in yet another embodiment, the solvent may be less than 35% of the total weight of the remaining rnaterial. in another embodiment, a substantially dehydrated binder has between about 10% and about 35% water by weight of total binder. In another embodiment, the solvent may comprise less than about 20% ofthe total weight of the remaining material. 1019] In illustrative embodiments, an uneured binder may be colorless, white, off white, ochre or yellow to brownish sticky substance that is, at least partially, water soluble. As used herein, the term cured binder describes the polymeric product of curing the uncured binder composition. The cured binder may have a characteristic brown to black color. While described as brown or black, another characteristic is that the binder tends to absorb light over a broad range of wavelengths, In particular, there may be higher absorbance at approximately 420 rnm, As the polymer is extensively cross-linked, the cured binder is substantially insoluble, For example, the binder is predominantly insoluble in water, As described herein, the unured binder provides sufficient binding capacity to consolidate fibers; however, the cured binder imparts the robust, long-lasting durability and physical properties commonly associated with cross-linked polymers. [0201 In illustrative embodiments, the binder reactants described herein tre soluble in water and the binder solution is a solution of the binder reactants in an aqueous solution. In one embodiment a surfactant is included in the aqueous solution to increase the solubility or dispersability of one or more binder reactants or additives. For example, a srfetanm may be added to the aqueous binder sokttion to enhance the dispersibility of a pariulate additive, In one embodiment, a surfacetant is used to create an emulsion with a non-polar additive or binder reactant. in another embodiment, the binder solution comprises about 0.01% to about 5% surfakctant by weight based on the weight of the binderolution. 10211 In illustrative embodiments, the binder solutions described herein can be applied to mineral fibers (e.g., sprayed onto the mat or sprayed onto the fibers as they enter the forming region), during production of mineral fiber isulation products, Once the binder solution is in contact with the mineral fibers the residual heat from the mineral fibers (note that the glass fibers, for example, are made from molten glass and thus contain residual heat) and the flow of air through and/or around the product will cause a portion of the water to evaporate from the binder solution. Removing the water leaves the remain cmponents ofthe ind onhe fibes as a coating ofviscous or semiviscous high-oids mixture This coating of cous or sem-viscous high-solids mature fncions as a binder At this poin Wthema has not been cured. In other rd the uneued binder functions to bind the fibers in the mat. [0221 Furthermore, it should be understood that the above described uncured binders can be cured. For example, the process of manufacturing a cured insulation product may include a subsequent step in which beat is applied as to cause a chemical reaction in the uncurod binder composition. For example, in the ease of making fiberglass insulation products, after the binder solution has been applied to the fibers aid dehydrated, the uncured insuladon product may be transferred to a curing oven in the curing oven the uncured insulation product is heated (e.g, from about 300 F to about 600 0 F [from about 150 0 C to about 320 C]), causing the binder to core. The cured binder is a formaldehyde-free, waer-resistant binder that binds the glass fibers of the insulation product together. Note that the drying and thermal curing may occur either sequentially, simultaneously, contempnoraneouislv, or concurrently. 10231 In illustrative embodiments, an uncured fiber product comprises about 3% to about 40% of dry binder solids (total uncured solids by weight). in one embodiment, the uncured fiber product comprises about %o about 2% of Qhy binder solds in another ebodiment the uncured fber prdUt comprise alnut 50% to about 97% fibes by weight 10241 Asentioned hereinwi respecta binder on mineral fibers aered binder is the product of curing binder reacants. The tern curd indicates that the under has een exposed to condions soa s tonitiate a chemeaehange Eamplesof these chemical changes include, but are not limited to, i) convent bonding, 6i) hydrogen bondingohf binder components, andf iii) chemically cross lig the polymers andor oligomers in te binder. ese changes mayincreasthe binden dtability und silent resistance as compared to the uncuredider Curing a binderrmy resuinthe formation of a thermaet material. in addition, a cured binderay res in an increase in adhesion between the atater in a collecton as cmpared toanm nend hidr uingcnb inittd byoreamlhea micr eradaion andmr condtinthat initiate owner more" oth chemical changes menoned bo. While not united to a particular theory, cring may include the reaction othe cbohydrate and the nuleophile in a nucleophili addition reactionor nuccophiic addition-ininationraction, 025 In astuaton where the chemicalhangeithe binder results in the release of water, g pomeriation and crosslinking a cure can be determined by Othe amount of watereased abovthat which would occur fromdying alon The techniqueused to msure theanunt ofater relasedduring ing as compared to when a index is cured arc we known in e art. 1026 in AuNstraive embodiment the nuaophilis a nitrogen containing conpound.I n one 'mbodimentthe cured binder compositin comprises a ntgenous polner In one embodime the genoupolerbrown tobl in color While notlimied toa partiular theorthecured binder composition comprises a Nxture of high molecular weight polymers. The hih molecular weight polymers may be characterized as being highly cross-linked. Furthennure, the high molecular weight pOlymfers may be characterized as being brown, complex. furan ring-containing and nitrogen-containing polymers. High molecular weight, as used herein, includes those polymers having a molecular weight in excess of 100,000 Daltons. Being comprised of highly cross-linked polymeric chains, the molecular weight of the high molecular weight polymers described herein approaches infinity. Accordingly, the molecular weight of the high molecular weight polymers may he a function of the mass and phys ical dimensions of the polymer being analyzed. For example, a unitary sample of melanoidins having a mass of 3 grams may be presumed to comprise a single polymeric molecule due to the extensive cross linking. Accordingly. the molecular weight of the polymer would be approximately LS x 1024 grams per mole (being the product of the sample mass and Avogadro's number), As used herein, a high molecular weight polymer includes polymers with a molecular weight in the order of between about I x I and bout Ix 24 [0271 While not be limited to a particular theory, it is understood that high molecular weight polymers vary in structure according to the reactants and conditions of preparation, It is also known that high molecular weight polymers possess a carbon to nitrogen ratio which increases with temperature and time of healing, Furthermore, high molecular weight polymers possess saturated, unsaturated and aromatic character, in one embodiment, the high molecular weight polymers possessed a degree of unsaturation and aromaticity that increased with temperature (cure temperature) and time of heating (cure time), The high molecular weight polymers also contained the Ci- of those sugars incorporated as reactants in a variety of structures within the polymer. The high molecular weight polymers may also contain carbonyl, carboxyl, nine, amide, pyrrole, indole, azomethine, ester, anhydride, ether, methyl and/or hydroxyl groups. Depending on the complexity of the structure, infrared spectroscopy may be useful in the identification of one or more of these futnetional groups, While not so classified here, one of ordinary skill would appreciate that the binder may be classifiable according to the existence of a particular bond present such as a polyester. polyether, polyamide, etc. [0281 Another manner in which the binder is characterizable is through analysis of the gaseous compounds produced during pyroysis of the cured binder. Gas pyrolysis of a cured binder within the scope of the present disclosure may yield approximately 0.5 to about 15% (by relative peak area) of one or more of the following compounds: 2-cyclopenten-1 one, 2,5-dimethyl-furan, furan, 3.

mthyl-25-furandionc, phenol., 2,3-dimothy-2-cyeiopcntn -one, 2-methyl phenol, 4-methyl phenol 2,4- dimethyl-phenol, dimethylphthalate, octadecanoic acid, or erucylamide, Fingerprinting in pyrolysis gas chromatography mass spectrometry (Py GC-MS) carried out at 770 *C of a binder sample prepared using hexamethylenediamine as the polyamin coUnponent shows pyidine and a number of components which are pyrrole or pyridine derivatives (a methyl pyridine, a methyl pyrrole, dimethyl pyridines, a dimethyl pyrrole, an ethyl methyl pyrrole, and other pyrrole related N-containing components), Another manner in which the binder may be identified is whether a solution ontaining the binder (or an extract soution) is capable of reducing Benedict's reagent. In one embodiment, a solution in contact with the binder or an aqueous extract thereof r .Benedict's reagent, [0291 One aspect of the present disclosure is that the binders described herein are environmentally friendly, Parallel to advancing government regulation, the present disclosure describes a binder that may be made formaildehyde-free. Additionally, the chemistry described herein is essentially free of formaldehyde and phenol. In this sense, neither formaldehyde nor phenol is used as a reagent within the scope of the present disclosure. While both may be added to obtain a binder with potentially usefd properties, one aspect of the present disclosure is a binder that can be made free from both of these reactants, in another aspect the present binder composition may be manufactured without the use of volatile reactants, in one embodiment, the nucleophile and the carbohydrate are both non volatile reactants. As used herein, a volatile reactant is one that has a vapor pressure greater than 10 kPa at 20 CC. Similarly, as used herein, a non-volatile reactant has a vapor pressure of less than about 10 kPa at 20 C. Specifically and as an example, the present binder may be manufactured without the addition of ammonia or an ammonia releasing compound. In one embodiment, the nucleophile has a vapor pressure of less than about 0,5 kPa at 60 -C. [030] Another environmentally friendly aspect of the present disclosure is that the primary reactants of the hinder are carbohydrates Carbohydrates are considered a renewable resource. However, the current state of the art primarily uses petroleum-derived reactants for the manufacture of binder compositions. n another aspect, the binder is made through chemical reactions which can occur at lower temperatures than those comparable systems described in the prior art, As such, the curing ovens and manufacturing equipment can be operated at lower temperatures, saving valuable resources. In the alternative and in a related manner, the binder described herein ctres more quickly than comparable binders currently used when subjected to similar curing temperatures, Accordingy, through either approach, one aspect of the present disclosure is that the carbon footprint of a formed product using the presently disclosed binder may be substantially reduced compared to a comparable binder made according to the current state of the art, for example a phenol formaldehyde based product. [031, In addition to the environental benefits, the present binder composition and materials made therewith cart be made having performance characteristics equivalent or exceeding those of comparable binder systems, for example, phenol formaldehyde binders, in one aspect, a binder according to the present disclosure provides articles made therewith suficient 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 water hold-up (weatherabilitv) comparable to that of a phenol formaldehyde binder, Other performance characteristic that nay be relevant for a particular application include product emissons, density, loss on ignition, thickness recovery, dust, tensile strength, parting strength, durability of parting strength, bond strengh, water absorption, hot surface performance, corrsivty o s~el, lex ra iidity sife-rgidity, comnpressive resistance, conditioned compressive resistance, compressive modulus, conditioned compressive modulus, and smoke development on ignition. One aspect of the present disclosure is that the extract of the cured binder is essentially pH neutral, for example between a pH of 6 and 8. Another aspect of the present disclosure is that the present binder enables the manufacture of products having comparable relevant performance characteristics to phenol formaldehyde binder compositions, 10321 Iustratively, in one embodiment, a binder according to the present disclosure invention has the advantage of yielding essentially colorless aqueous extracts. This feature of the present disclosure makes the binder desirable in applications such as ceiling tiles, furniture, or offe panels, wherein the finished product mny come into contact with water. A cured manufactured good made with the present binder shows an excellent resistance to discoloration or bleeding after coming in contact with moisture or water. Furthermore, in such an embodiment, the water that contacts the binder does not leave a residual color on other articles or parts which it may contact subsequei to contact the binder. For example, in one embodiment, the binder may be used to bind glass fibers in an office panel application. Covering th bound fiberglass composition may bc a light colored fabric. Advantageously, in one embodiment, water contacting the fiberglass composition does not leave a colored residue upon the fabric after the offce panel has dried. [033} In addition to the performance characteristics, the manufacturing processes and methods involving the presently disclosed binder have a number of unexpected advantages over previously described binders. In one aspect, as previously described with respect to the environmental benefits, the present binder may be manufactured without the use of highly volatile reactants. Accordingly, manufaciui-ing emission controls are under a reduced burden. Furthermore, tile reaction efficiency is higher because reactant loss due to vaporization is reduced. Accordingly, one aspect of the present disclosure is that the compounds uscd herein are substantially non-volatile, thus the steps one must take to ntigate undesirable emissions are reduced. [034] According to another aspect, the reactants that react to form a binder are sufficiently slow to react such that a one step/one pot binder system can be used. According to this aspect, the reactant compounds are sufficiently slow to react that they can be added to a single reactant solution and stored for a reasonable amount of time during which they can be applied to a product using one distribution system. This contrasts with those binder systems which react at low temperatures resulting in insoluble reaction products within binder solution delivery systems. As used here, a reasonable amount of tin for storage without substantial (>S%) polymeric precipitation is two weeks, [035] Another aspect of the present disclosure is that, although the binder is sufficiently unreactive at room temperature conditions to facilitate a one-pot approach, it is stuficicntly reactive at elevated temperatures to cure at very low temperatures and/or very short curing residency tints, In one respect, the lowered curing temperature reduces the risk of an insulation product undergoing flameless I 0 combustion and/or causing line 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 mi. 1036] Tn irmstra.ive ebodiments, the binder composion includes an acid or an acid sat to increase the shelf life of the uncured binder or binder solution. While this acid is not a reactant or a catalyst, it may be included to slow or inhibit the binder reactants from forming the binder while the binder solution or uncured binder is being maintained under storage conditions, For example, a volatile acid or acid salt may be included in the binder solution or uncured binder that slows or inhibits the curing reaction at ambient conditions, However, the acid may be removed by heating the binder solution or uncured binder so that the acid is volatilized and the pH of the binder solution or uncured binder increases. I one embodiment, the binder composition includes a shelf-life extending acid In another embodiment, the binder composition includes a mole ratio of shelf-ife extending acid to nucleophile of about 1:20 to about 1:1. A0371 Another aspect of the present disclosure is a binder having a cure rate, cycle time, and cure temperature which meets or eceeds those cure rates that a comparable phenol and formaldehyde type binder may exhibit within the scope of a comparable use, in this respect, the present binder can be used as a direct replacement to phenol formaldehyde resins in applications without modiication to the equipment. Furthermore, the present binder enables the modification of the curing temperature and times so that both the reaction temperatures and cure times may be reduced. This reduction has the effect of reducing the energy consumption of the process overall and reduces the environmental impact of manufacturing the product. Furthermore, the lower cure temperatures have the further effect of increasing the safety of manufacturing process. Another effect of the lower cure temperatures is a reduction in the risk of flamieless combustion or fire. 038 In the manufacture of insulation products, the heat released by the exothermic curing reaction may result in self-heating of the product. Self-heating is typical not problematic so long as the heat dissipates from the product, However, if the heat increases the temperature of the product to the point where oxidative processes commnence, the self-heating may cause significant damage to the product For example, flaneless conbustion or ox ideation may nccur when the temperature of the insulation product exceeds about 425 *F (210 *C) At these temperatures, the exothermic combustion or oxidation processes promote further self-hearing and the binder may be destroyed. Furthermore, the temperature may increase to a level in which fusing or devitrification of the glass fibers is possible. Not only does this damage the structure and value of the insulation product, it may also create a fire hazard, [039] 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 sals thereof as catalyst or active ingredient, Accordingly, one aspect of the present binder is that it may be made essentially acid-free. Furthermore, the binder may be manufactured under entirely alkaline conditions As used here, the term acid includes those compounds which arc characterizable primarily for their acidic character such mtiprotic inorganic and organic acids (e.g. sulfuric acid and citric acid). This aspect reduces the wear and maintenance requiremems of the manacturing equipment and enhances worker safety. 0401 i lustratve embdnments, a binder comprises a polymeri roduct of a carbohydrate reactant and a nucleophile. As used herein, the term carbohydrate reactant refers to a monosaccharide, a disaccharide, a polysaccharide, or a reaction product thereof. In one embodiment, the carbohydrate reactant may be a reducing sugar. As used hercin, reducing sugar indicates one or more sugars that contain aldehyde groups, or that can isonerize, i.e., tauromerize, to contain aldehyde groups, which groups may be oxidized with, for example, Cu 2 to afford carboxylic acids. It is also appreciated that any such carbohydrate reactant may be optionally substituted, such as with hydroxy, halo, alkyl, aikoxy, and the like. It is further appreciated that in any such carbohydrate reactant, one or more chiral centers are present, and that both possible optical isomers at each chiral center are contemplated to be included in the invention described herein. Further, it is also to be understood that various mixtures, including racemic mixtures, or other diastereomeric mixtures of the various optical isomers of any such carbohydrate reactant, as well as various geometric isomers thereof, may be used in one or more embodiments described herein. While non-reducing sugars, for instance sucrose, may not be preferable, they may none-the-less be useful within the scope of the present disclosure by in-situ conversion to a reducing sugar (ie. conversion of sucrose to invert sugar is a method known in the art). Further, it is also understood that a monosaccharide, a disaccharide. or polysaccharide may be partially reacted with a precursor to form a carbohydrate reaction product. To the extent that the carbohydrate reaction prodnet 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 nueleophile, the carbohydrate reaction product is within the scope of term carbohydrate reactant. [04 1 in one aspect, any carohydrate reactant should be sufficieMnly nonvolatile to maximize its abilHy to remain available for reaction with the nucleophile. The carbohydrate reactant may be a monosaceharide in its aldose or ketose formn, inchding a trinse, a trrose, a pentose, a hexose, or a heptose; or a polysaccharide; or combinations thereof For exarnple, when a triose serves as the carbohydrate reactant, or is used in combination with other reducing sugars and/or a polysaccharide, an aldotriose sugar or a ketotriose sugar may be utilized, such as glyceraldehyde and dihydroxyacetone, respectively. When a tetrose serves as the carbohydrate reactant, or is used in combination with other reducing sugars and/or a polysaccharide, aldotetrose sugars, such as ervthrose and threose; and ketotenose sugars, such as erythrulose, many be utilized. When a pentose serves as the carbohydrate reactant, or is used in combination with other reducing sugars and/or a polysaccharide, aldopentose sugars, such as ribose, arabinose, xylose, and lyxose; and etopeose ugars, such as ribulose, arabulose, xylulose, and lyxulose, may be utilized. When a hexose serves as the carbohydrate reactant, 12 or is used in combination with other reducing sugars and/or a polysaccharide, aldohexose sugars, such as glucose (Le, dextrose), mannose, galactose, allose, altrose, talose, gulose, and idose; and ketohexose sugars, such as fructose, psicose, sorbose and tagarose, may be utilized, When a heptose serves as the carbohydrate reactant, or is used in combination with other reducing sugars and/or a polysaccharide, a ketoheptose sugar such as sedoheptulose may be utilized Other stercoisomers of such carbohydrate reactants not known to occur naturally are also contemplated to be useful in preparing the binder compositions as described herein. in one embodiment, the carbohydrate reactant is high fructose corn syrup. 10421 in illustrative embodiments, the carbohydrate reactant is aplysaccharide in one embodiment, the carbohydrate reactant is a polysaccharide with a low degree of polymerization. In one embodiment, the polysaccharide is molasses, starch, cellulose hydrolysates, or mixnres thereof, In one embodiment, the carbohydrate reactant is a starch hydrolysate, a Inaltodextrin, or a mixture thereof While carbohydrates of higher degrees of polymerization may not be preferable, they may nonethe-less be uselC within the scope of the present disclosure by in-situ depolymerization (i.e. depolymerization through armoniation at elevated temperatures is a method known in the art) 1043] Furthermore, the carbohydrate reactant may be used in combination with a non carbohydrate polvhydroxy reactant Examples of non-carbohydrate polyhydroxy reactants which can be used in combination with the carbohydrate reactant include, but are not limited tmethylolpropane, glycerol pentaerythritol. polyvinyl a lcohol, partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinyl acetate, and mixtures thereof In one aspect, the non-carbohydrate polyhydroxy reactant is suffeiently nonvolatile 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 reactant may be a actor in determining the physical properties of a binder prepared as described herein, [0441 As used herein, a nueleophile is a reagent that forms a bund to its reaction partner (the electrophile) by donating both bonding electrons. As used herein, an eletrophile is a reagent that forms a bond to its election partner (the nucleophile) by accepting both bonding electrons from that reaction partner. Illustratively, the electrophile is the carbohydrate described herein Specifically, tbe electrophilic group is the carbon associated with the aidose or ketose form of the carbohydrate. For example, C-1 of glucose is electropositive due to the aldose functionality and reacts with a nucleophi I of the present disclosure. in another example, C2 of fructose is electropositive due to the ketose functionalty and reacts with a nucleophile of the present disclosure. While described as an electrophile in its initial interaction with the nucieophile, one skilled in the art will appreciate that the carbohydrate is not limited to acting only as an electrophile witi the scope of reactions which may occur. For example, the hydroxyl groups of the carbohydrate may act as a nucleophile depending on the presence of a reactive nucleophile. Furthermore, while the initial reaction between the nucleophile and the -13carbohydrate may corr cssi he carbohydrate as an electrophile, the product of that reaction ay exhibit both nulclophilic and ciectrophilic functionality in further reactions. [045j In ilhsrative embodiments, the nuclcophile is sufficiently nucleophilic to react with a carbohydrate in its aldose or ketose form in a solution having a pH as desried 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 nueleophile which stabilizes the cation that forms upon the nueleophilic attack, For example, one nuclcophile within the scope of the present disclosure is a dianine. Upon nucleophilic attack of a carbonyl by a primary a-mine, a cation of a Schiff base is formed, While the diamine's first amine acts in the role of a nueleophile, the second amine acts in the role of a cationic stabilization moiety as it stabilizes the cation of the Schiff base, Further rearrangement of the cation of the Schiff base to the enol or keu form is known to proceed spontaneously, Th be ation that forms upon nucleophilic attack is similarly stabilized (as a Schi ff base is) by the structure of the nucleophile. in another aspect, the structure of the nucleophile accelerates rearrangement by stabilizing the positive charge that is acquired while the compound is in the form of a cation that forced upon nucleophilic attack, 1046) It was discovered that this spontaneous reaction is further facilitated by dehydration, as the rate was increased in dehydrated samples. It is believed that the importance of the stabilization moiety has not been discussed in the prior art within the scope of the present application as the enhanced effect of using a nueleophile of the present disclosure has not previously been disclosed. Accordingly, one aspect of the present disclosure is that the nucleophile is of a type that provides stability to a cation of a nucleophilie base during a subsequent rearrangement. In another aspect, the nucleophile is of a rype that provides stability to a cation of a nucleophilic base during a subsequent rearrangement while in a substantially dry state, [047I in illstrative embodiments, the nucophile is R -Q-R 2 , wherein Q is alkyl, Cvlolkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted, R 1 is a nucleophilie moiety, and R, is the stabilization moiety. In one embodiment, R 1 is selected from the group consisting of an amine, an azide, a cyanate, an isocvanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carhoxyl, a earboxylate, a hydroxyl, and an alkoxide, in another embodiment, R2 is selected from the group consisting of an amine, an ami an an iminean n imide, a nitro, a nitrate, a yridie, a phosphate, a phosphono, a hydro a hya hydrogen, a sulphon, a sulpho, a sufinyl, and a sulfhiydryl (thiofl) I4S in one em n nt, thnudeophile e a primary amine. As used hrein, a pima amone i an organic compound having one more primary ane groups. With ih"e scope of h tem prmr amne are dhoe compounds -ch can be modified in s or somerize to geerate a compound hing on or nore prmary amine gEups., 1inne embodient thepma amine be a moAcule having t frula of H$N -Q-, whereQin is ai kyl cyokyl, haeteol or cycloheteroalkyl, each of which may be optionally subsituted and R includes a cationic stabilization moiety selected from the group consisting of an aminn ami amide, an iminean a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a suiphono, a sulpho, a sulfinyl, and a sulfhydryl (thiol). [049] In one embodiment, Q s an aikyl selected from the group consisting of Cr024. in another embodiment, Q is an aliy selected from the group consisting of CC8. In another embodiment, Q is an alkyl selected from the group consisting of C3-C7. In yet another embodiment, Q is a C6 alkyl. in one embodiment, Q is selected from the group consisting of a cyclohexyl, cyclopentyl or cyclobuivyl In another embodiment, Q is a benzyl In one embodimert, R -Q-R 2 is 2-(2 aminoethyl)aminojethanoi. In another embodiment of R 1

-Q-R

2 . each of Rj and .R2 is thiol. In one embodiment, R 1 is an amine, In a further embodiment of the above, is an amine, an amide, an inine, or an imide. In a further embodiment of the above, R 2 is an amine. [0501 As used herein, the term alkyll" includes a chain of carbon atoms, which is optionally branched. As used herein, the term "alkonyl" and "alkynyl" includes a chain of carbon atoms, which is optionally branched, and includes at least one double bond or triple bond, respectively. it i to be understood Ihat alkynyl may alo include one or more double bonds. It is to be further understood that aikyl is advantageously of limited length, including C a Cr'C-3' Cr-0s, CvC'. and QC4. 1 is to be further understood that alkenyl and/or alkynyl may each be advantageously of limited length, including C2c4 C1C Cr~s, C>, and C.-(', it is appreciated herein that shorter aikyl alkenyl, and/or alkynyl groups may add less hydrophilieiy to the compound and accordingly will have different reactivity towards the carbohydrate reactam and solubility in a binder solution, 10511 As used herein, th term'cycloalkyl" includes a chain of carbon atoms, which is optionally branched, where at least a portion of the chain in cyclic It is to be understood that eycloalkylaikyl is a subset of cycloalkyl It is to be understood that cycloalkyl may be polycyclie. Illustrative ev yloalkyl include, but are not limited to, cyclopropyl, cyclopentyL. cyclohexyl, 2 merthylcyclopropyl, cyclopentyleth-2-yl, adamantyl, and the like. As used herein, the term "cycloalkenyl" mnludes a chain of carbon atoms, whieh is optionally branched, and includes at least one double bond, where at least a portion of the chain in cyclic. It is to be understood that the one or more double bonds may be in the cyclic portion of eyeloalkenyi and/or the non-cyclic portion of eycloalkenyL It is to be understood that cycloalkenylalkyl and cycloalkylaikenyl are each subsets of cycloalkenyl It is to be understood that cycloalkyl may be polycyclic. Illustrative cyclealkenyl include, but arc not limited to, cyciopentenyl cyclohexylcthen-2.yl, cycloheptenvlpropenyi and the like. it is to be father understood that chain forming cycloalkyl and/or cycloalkenyl is advantageously of limited legtih, including Cr-C Q Cr CCrOr, Cr- and Cr7s It is appreciated herein that shorter alkyl and/or alkenyl chains forming cycloalkyl and/or cycioalkenyl, respectively, may add less lipophilicity to the compound and accordingly will have different behavior.

[052j As used herein, the term "heteroalkyl" includes a chain of atoms that includes both carbon and at least one heteroarom, and is optionally branched. Illustrative heteroatoms include Mrogen, oxygen, and sulfur. In certain variations, illustrative hetcroatoms also inhclde phosphorus, and selenium As used herein, the term "cycloheteroalkyl" including heterocyciyl and heterocycle, includes a chain of atoms that includes both carbon and at least one hieternator, such as heteroalkyl, and is optionally branched, where at least a portion of the chain is cyclic. Illustrative heteroatons include nitrogen, oxygen, and sulfur. In certain variations, illustrative hoteroatoms also include phosphorus, and selenium. Illustrative cycloheteroalkyl include, but are not limited to, tetrahydofuryl, pyrrolidinyl, tetrahydropyranyt, piperidinyt, morphoinyl, piperazi nyl, homopiperazinylt quinuclidinyl, and the like. [053] The term "optionally substituted" as used herein includes the replacement of hydrogen atoms with other functional groups on the radical that is optionally substituted Such other ftmucional groups illustratively 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. ilstratively any ofamino, haloalkyl, heteroalkyl, aryd, arylalkyl, arylheteroalkyl, and/or sulfonic acid is optionally substituted 10541 In illustrative embodiments, the nucleophile is a diamine, triamine, tetraamine, or pentamine. In one embodiment, the polyanc is a triamine selected a diethylenetriamine, 1~ piperazineethaneamine, or bis(hcxanethvlenep-ianine, In another embodiment, the polyamine is a tetramnine, for example triethyleneletramine. in another embodiment, the poiyamine is a pentamnine, for example tetracthiylenepentamine. (055J One aspect of the nucleophile is that it may possess low steric hindrance. For example, Q is selected such that the nucleophile has low steric hindrance, For example, if Q is essentially linear and has a length of at least three atoms, the nucleophulic moiery and the stabilizing Oiety are sufficiently spaced so that the nucleophile is able to react with the electrophile, [0561 While not being limited to a particular theory, the stabilization moiety is so called because it may stabilize a reaction intermediate as described herein, However, in another aspect of the present disclosure, the stabilization moicty may also serve as a reactant within the scope of the present disclosure. As such, rearrangement products existing after the reaction between the nucleophilic moiety and the cas bohydrate may convert or return the stabilization moiety into a group that reacts or is capable of reacting with another carbohydrate. Accordingly, the stabilization moiety may convert or return to the for of a nucleophilic moiety and react with the carbohydrate accordingly, In illustrative embodintrs, the Q group, as described herein, can serve to isolate the two groups suhthat R1and Raresntayunafifeeted by the chemistry occurringa h te suc h 3 R"' R- are esenial u ng at The other position. As such, the Q group may or may not be serving in the capacity of a stabilization moiety. According to this theory, the advantages gained through utilization of a (idnctional nucleophile are attrbutable primarily to the fact that a single di-fumtional compound can form a cross-link between two carbohydrate compounds. Because the two functional groups are linked through a Q group, upon reaction of both R 1 and R2. the result is a higher molecular weight product than if R1 and R were not linked through the () group. As such, the Ifl and R2 can be selected from the group consisting of an amine, an azide, a cyanate, an isocyanae, a thioL a disulfide, a Lhiocyanate, a halogen, a haloformyl, a carboxyl a carboxylate, a hydroxyl, an alkoxide, an amide, an imine, an imide, a nitro, a nitrate, a pvridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulphono, a sulpho, a sulfinyl, and a sulfhtydryl ('thi ol), [057] in illustrative embodiments, the Q group is of the type which enables the chemical communication between Rl and R2. For example, Q may enable chemical communication by enabling resonance and polarity shifs from R1 to 112 In other embodiments, Q may be of a length that reactions at either Rj and R2 cause changes to the electron distribution at the other group (R or R2% In one embodiment, the nucleophile includes a stabilization moiety and a nucleophilic moiety. in one embodiment, the nucleophilic moiety is selected from the group consisting of an amine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanaite a halogen, a halofornl, a carbcxyl, a carboxylate, a hydroxyl, and an alkoxide. In another embodiment, the cationic stabilization moiety 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 sulphono, a sulpho, a sulfmnyl, and a sulihydryl (thiol), [05Sf In one embodiment, the nucleophile may include a polymeric polyamine, For example, polymeric polyamines within the scope of the present disclosure include chitosan, polylysine, polyethyienimine, poly(N-vinyl-methyl amine), polyaminostyrene and polyvinylamines, in one embodiment, the polyaiine comprises a polyvinyl amine, As used herein, the polyvinyl amine can be a homnopolymer or a copolymer. [0591 While not limited to a particular theory, one aspect of the present disclosure is that the primary amine and the carbohydrate reactant are Maillard reactants that react to form a melanoidin product, Fig. I shows a schematic of a Mailiard reaction, which culminates in the production of melanoidins, in its initial phase, a Maillard reaction involves a carbohydrate reactant, for example, a reducing sugar (note that the carbohydrate reactant may come from a substance capable of producing a reducig sugar under Maillard reaction conditions), The reaction also involves condensing the carbohydrate reactant (e.g, reducing sugar) with an amine reactant, t e, a compound possessing an amino group. in other words, the carbohydrate reactant and the amine reactant are the mclanoidin reactants for a Maillard reaction. The condensation of these two constituents produces an N-substituted glycosylamine. For a more detailed description of the Maillard reaction see, Hodge,.L E. Chemnisry of Browning Reactions in Model Systems J Agric. Food Chem 1953, 7, 928~943. the disclosure of which is hereby incorporated herein by reference. The literature on Mailiard reactions focuses on a melanoidins produced from amino acids, The present disclosure can be distinguished from these references in that the nucleophiies within the scope of the present disclosure also include a stabilization moiety. Common a mino acids which are considered within the scope of the preset disclosure include asparagine, glutamine, histidine, lysine, and arginine. 10601 Without being bound to theory, the covalent reaction between the nucleophile and the carbohydrate reactant will be described in greater specificity. As described herein, the pathway of the present reaction is distinct from those taught in the prior art for the following reasons: (1) the present reaction may occur completely at basic pH, (2) the nucleophile is difuntional having a nucleophiic moiety and a stabilization moiety, (3) the nucleophile, through its di-functionality or another unrecognized pheinena, exhibits a lower activation energy within the scope of the reaction which results in an unexpected increase in reaction rate and/or a decrease in the temperature at which the reaction will proceed. [0611 in illustrative embodiments the first step i tb formation of high molecular weight polymers from a nucleophile and a carbohydrate reactant is the condensation of the carbohydrate reactant and the nucleophile. Evidence indicates that the conditions described herein arc especially suitable for driving this reaction to completion, First, it is believed that the alkalinity of the binder solution drives the condensation, For example, it has been shown that sugars and nueleophiles such as amines undergo browning in aqueous solution in proportion to the basic strength of the amines employed or the pHi of she solution. In this example, it is believed that the N-ubstituted glycosylamines remain tndissociated in aqueous solutions to appreciable extent. Thus, the irreversible transformations that the undissociated molecules undergo must be considered. While it is known that the condensation reaction is reversible, we discovered that this reaction can be Iurther driven to completion, in accordance with Le Chatelier's principle by the concurrent dehydration of the binder solution. As such, it was established that initially a primary constituent of the uneured binder composition was the condensation products of the ncleophile and the carbohydrate. 10621 The second step in the conversion of the binder reactants to high molecular weight polymer products may be a rearrangement, An exemplary rearrangement is shown as a schematic of a Ainadori rearrangement in Fig. 2, Referring to Fig. 2, the N-glyosyl derivatives of the representative amines are in equilibrium with the cation of a Schiff base. While this equilibrium favors the Nglycosylamine, further rearrangement of the cation of a Schiff base to the enol or keto form is known to proceed spontaneously, It was discovered that this spontaneous reaction is further facilitated by dehydration, as the rate was increased in dehydrated samples. One aspect of the present disclosure is that the structure of a nucleophile specifically acce lerates thts rearnmgement by stabilizing the positive charge that is acquired while the compound is in the form of a cation of a Schiff base. t is believed that this stabilization effect has riot been discussed in the prior art or the literature as the enhanced effect of using a nucleophile as such within the scope of the mesent disclosure has not previously been disclosed, Accordingly, one aspect of the present disclosure is that the nucleophile is of a type that provides stability to a calionic base during a rearrangement in another aspect, the nucleophile is of a type that provide stability to a cationie base during a rearrangement while in a substantially dry state. [0631 Another aspect of thc present disclosure is that the carbohydrate structure is also believed to influence the kinetics of the rearrangement. Specifically, it is known when the 0-2 hydroxyl of a crystalline N-substituted glycosylamine was unsubstituted, the compound was slowly transformed dung storage to the rearrangement product. However, if the 0-2 hydroxyl was substituted, then the rearrangement was substantially inhibited. Accordingly, one aspect of the present disclosure is that a carbohydrate of the present disclosure is unsubstituted at the hydroxyl adjacent to the ketone or aldehyde, 10641 In illustrative embodimems, the molar ratio of the carbohydrate reactant to the nucleophile is in the range of about 1:1 to about 301. In another embodiment, the molar ratio of the carbohydrate reactant to the nucleophile is in the range of about 2:1 to about 10:1. in yet another embodiment, the molar ratio of the carbohydrate reactant to the nucleophle is in the range of about 3:1 to about 61 According to one aspect, the cure rate is a function of the molar ratio of the carbohydrate reactant to the primary poIyamine, According to this function, it was established that as the ratio decreased, the cure rate increased; thus the cure time decreased. Accordingly, the one aspect of the present disclosure is that the cure time is directly related to the molar ratio of the carbohydrate reactant to the polyanine provided that other parameters are held equivalentIn another aspect, the binder cure time is reduced to the cure time of a comparable phenol formaldehyde hinder composition when the molar ratio of the carbohydrate reactant to the nucleophile is equal to about 1 Accordingly, in one embodiment, a binder according to the present disclosure has a cure rate exceeding a comparable phenol formaldehyde binder system when the carbohydrate reactant to nucleophile molar ratio is in the range of about 2:1 to about 6:1. (0651 Another aspect of the reaction, as described herein, is that initially the aquteus reactant solution (which may be dehydrated and used as a. binder) has an alkaline pH. One aspect of the present disclosure is that the alkaline binder solution is less corrosive towards metal than acidic solution, Accordingly, one nature of the present disclosure which overcomes a substantiad barrier to the industry is that the binder described herein has low corrosivity towards the manufacturing equipment which may be used to produce materials which include the present binder because of the alkaline binder composition. One distinguishing feature of the present disclosure over other recently described carbohydrate binder systems (eg. US. Published Application No. 2007/0027283), is that the reaction dees not necessarily proceed through an acidic pathway. Rather, one aspect of the present disclosure is that the uncured binder may have an alkaline pH throughout the course of the chemical reaction which leads to the formaton of the cured hinder, As such, the uncured binder, throughout its use and storage does not present a corrosion risk. n 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 the polymeric product is essentially colorless. [066j Tn illustrative embodiments, a method of making a collection of matter bound with a polymeric binder comprises preparing a solution containmg reactants fbr producing the polymeric binder and a solvent, wherein the reactants include a carbohydrate reactant and a nucleophile; disposing the solution onto the collection of matter; volatilizing the solvent to form atn uncured product, and sub jecting the uncured product to conditions that cause the carbohydrate reactant and the nucleophile to polymerize to form the polymeric binder, [067J In illustrative embodiments, the collection of matter includes insulating fibers. In one embodiment, a fiber insulation product is described which includes insulating fbers and a binder, As used herein, term "insulating fiber," indicates heat-resistant fibers suitable for withstanding elevated temperatures, Examples of such fibers include, but are not limited to, mineral fibers (glass fibers, slag wool fibers, and rock wool fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, certain polycster fibers, and rayon fibers, illustratively, such fibers are substantially unaffected by exposure to temperatures above about 120 CC. In one embodiment, the insulating fibers are glass fibers. In yet another embodiment, the mineral fibers are present in the range from about 70% to about 99% by weight. [0681 in illustrative embodiments, the collection of matter includes ceilulosic fibers. For example, the cellulosic fibers may be wood shavings, sawdust, wood pulp, or ground wood. In yet another embodiment, the cilulosicfIber imay be other natural fibers such as jute, flax, hemp, and straw. The binder disclosed herein may be used as in the place of The binder described in Published PCT application We 2008/089847, which is incorporated herein by reference in its entirety. In one embodient, a composite wood board compriaing wood particles and a binder is disclosed. In another embodiment, the composite wood board is formaldehyde free. In one embodiment, the composite wood board has a nominal thickness range of greater than 6 mm to 13 mm, and has a modulus of elasticity (MOE) of at least about 1050 N/mm 2 , a bending strength (MOR) of at least about 7 N/mm 2 , and an internal bond strength (1B) of at least 0.20 N/am In another embodiment, the composite wood board has a nominal thickness range of greater than 6 mm to 13 mm, and has a bending strength (MOR) of at least about 12.5 N/mm 2 , and an internal bond strength (iB) of at least 0.28 N/mm 2 , I another embodiment, the composite wood board has a nominal thickness range of greater than 6 mm to 13 mm, and has a modulus of elasticity (MOE) of at least about 1800 N/mm 2 , a bending strength (MOR) of at least about 13 N/mm 2 , and an internal bond strength (1B) of at least 0,40 N/mm 2 . in another embodiment, the composite wood board has a modulus of elasticity (MOE) of at least about 1800 N/mm2. In another embodimen, the composite wood board has a modulus of elasticity (MOE of at least about 2500 N/mm2. In another embodiment, the composite wood board has a bending strength (MOR) of at least about 14 N/mm 2 , In yet another embodiment, the composite wood board has a bending strength (MOR) is at least about is NANm 2 , In one embodiment, the composite wood board has an internal bond strength (1B) of at least 0.28 N/mn. in yet another embodiment, the composite wood board has an internal bond strength (TB) is at least 0.4 N/mn 2 . In yet another embodiment, the composite wood board swells less than or equal to about 12%, as measured by a change in thickness, afer 24 hours in water at 20 "C. In another embodiment, the composite wood board has a water absorption after 24 hours in water at 20 "C of less than or equal to about 40%. [069] In illustrative embodiments the composite wood board is a wood particleboard, an orientated strandboard, or a medium density iberboard. ln one embodiment, the binder comprises from aboul 8% to about 18% by weight (weight of dry resin to weight of'ry wood particles) of the composite wood board. In another embodiment, the composite wood board further comprises a wax. In yet another em:bodient, the composite wood board comprises from about 0.1% to about 2% wax by weight of the composite wood board. In illustrative embodiments, the method of making a collection of matter bound with a polymeric binder may further include preparing a solution by adding an amount of a carbohydrate reactant and an amount of a nucleophile so a molar ratio is in the range of about 2:1 to about 101. in one embodiment, preparing the solution includes adding the carbohydrate reactant and the polyamine to an aqueous solution. In another embodiment, preparing the solution includes adjusting the pH of the solution to within the range of about S to about 12. In yet another embodiment, the method of making a collection of matter hound with a polymer hinder may further comprise packaging the uncured product in a packaging material suitable for storage, 1070] 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 reactant and a nucleophile, the polymeric products being substantially water insolublc. in one enboditnet, the collection of matter includes mineral fbers, aramid fibers, ceramic fibers, metal fibers, carbon fibers polimide fibers, polyester fibers, rayon fibers, or cellulosic fbers. For example, cellulosic fbers may include wood shavings, sawdust, wood pulp, and/or ground wood. in one embodiment, the collection of matter includes sand or other inorganic particulate matter. in one embodiment, the collection of matter is coal particulates. in one enibodinment the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof, in ono embodiment, the nueleophile is R PQ-R2, wherein Q is alkyl, cycloalkyk heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted, Ri is a nucleophilic moiety, and R is a stabilization moiety. [071J In another embodienthe ctmposiunt fAther comprise a con compound in oe embodimmt the slon-conaing compound is a ftncionalized sIlylethe or a fuei nalized alkylsilether, such as for examplern ano nctnaized i rF exa ein one embodiment, the siaiconcotainncompndayga amninopropvytriethoxysilane gammna-glyidoxyropyl trmerhxsiaeor -21 aminoethylamninoproptltrimethoxysilane, or a mixture thereof In another embodiment, the silicon containing compound may be an amninofunctional oligomeric siloxanse. In another embodiment, the composition comprises a corrosion inhibitor selected from the group consisting of deducting oil, monoammonim phosphate, sodium netasilicate pentahydrate, melamine, tin (I1)oxalate, and a methylhydrogen silicone fluid ernuls ion. [072J In further illustrative embodiments, the binder may be disposed upon a collection of fibers substantially dehydrated, packaged, and then stored or sold to another party. An uneured product sold to another party for use in further manufacturing processes may be referred to as "ship-our uncured." An uncured product stored for use in further manufturin may b r to as "plant uncured. In selling or storing this type of product, it is packaged in suitable containers or bags. [0731 ln illustrative embodiments a packaged uncured fiber product comprises an uncured binder composition and a collection of fibers, wherein (i) the uncured binder composition is in contact with the collection of fibers consolidating the collection of fibers and (ii the uncured binder composition in contact with the collection of fibers is packaged in a suitable packaging material. In one embodiment, the amount of moisture in the uncured binder composition may be in a range from about 1% to about 15% by weight based on a total weight of the product. In yet another embodiment, the suitable packaging material may be capable of maintaining the amount of moisture in the uncured binder composition to within about 20% of an original moisture level for a period of one week at an ambient temperature and an ambient pressure. in one embodiment, the packaged uncured fiber product comprises front about 3% to about 30% by weight of the uncured binder composition based on weight of the packaged uncured fiber product without considering the weight of the suitable packaging material in one embodiment, the packaged uncured fiber product comprises forn about 60 to about 97% by weight fibers based on weight of the packaged uncured fiber insulation product without considering the weight of the suitable packaging material [0741 One aspect of the present disclosure is that the binder described herein is unexpectedly useful in applications ship-out tncured and plant uncured applications, Specifically, ship-out uncured products and plant uncured products are provided with an uncured binder so that the curing can occur at a later time and in a later place. In the case of ship-out uncured, the curing temperature and time are properties of the product which are of great importance to the customers. Specifically the cure temperatures must be suiciently low such that the product can he cured using their existing equipment Furthermore, the cure time must be suffciently short such that the cycle time for curing the products remains low. Within this industry, the manunhcturing equipment and acceptable cycle times have been established for uncured products comprising phenol forraldehyde type resins. Therefore, sufficiently low cure temperatures are those cure temperatures suitable for curing a comparable phenol formaldehyde type product. Similarly, sufficienly low cycle times are those cycle times which would be routine for curing a comparable phenol formaldehyde type product One of ordinary sill in the art 22 will appreciate that neither cure time nor cure temperature can be set forth as definite quantities because the specific applications may have dramatically different parameters. However, it is well understood that the cure time and cure temperatures of a model system provide sufficient represenative information regarding the kinetics of the underlying chemical curing reaction so that reliable predictions of binder performance in the various applications can be made [0751 in illustrative embodiments, the cure time and the cure temperature of the binder is equal to or less rhan a comparable pheol formaldehyde binder composition. in one embodiment the cure time of the binder is iess 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 temperature of a comparable phenol formaldehyde binder compositior. As used herein, a comparable phenol formaldehyde binder composition is like that described according to U.S. Parent No. 6,638,882, which patent is hereby incorporated by reference herein in its entirety. [076 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 silicon-containing coupling agent, Many silicon containing coupling agents are commercially available from the Dow-Corning Corporation, Evonik Industries, and Momentive Performance Materials, illustratively, the silicon-containing coupling agent includes compounds such as silylethers and alkylsilyl ethers, each of wtich may be optionally substituted, such as with halogen, alkoxy, amino, and the like. In one variation, the silicon-containing compound is an amino-substituted silane, such as, gamma-aminopropyhriethoxy silane (SILQUEST A 1101; Momentive Performance Materials, Corporate Headquarters: 22 Corporate Woods Boulevard, Albany, NY 122 I USA). In another variation, the silicon-containing compound is an amino substituted silane, for example, aminocthvlaminopropyltrimcthoxy silane (Dow Z-6020; Dow Chemical, Midland, Ml; USA). In another variation, the silicon-conaining compound is gamna glycidoxypropytrimethboxyslane (SILQUE ST A-187: Momnentive). In yet another variation, the silicon containing compound is si aninefunctional oligomeric siloxane (HYDROSL 2627, Evonik industries, 379 Interpace Pkwv, Parsippany, NJ 07054), 19771 The silicon-containing coupling agents are typically present in the binder in the range from about 0.1 percent to about 1 percent by weight based upon the dissolved binder solids (ie., about 0.05% to about 3% based upon the weight of the solids added to the aqueous solution), In one application, one or more of these silicon-containing compounds can be added to the aqueous binder solution, The binder is then applied to the material to be bourd Thereafter, the binder may be cured if desired. These silicon contai compounds enhance the ability of the binder to adhere to the matter the binder is disposed on suc as gls fibes Ehning th binder's ability to adhere to the matter improves, fbo example, its ability to produce or promote cohesion in non- or loosely- assembled substancess, [078 in another illstrative embodiment, a binder of the present invention may include one or more corrosion inhibitors. These corrosion inhibitors prevent or inhibit the eating or wearing away of a substance, such as, metal caused by chemical decomposition brought about by an acid. When a corrosion inhibitor is included in a binder of the present invention, the binder's corrosivity is decreased as compared to the corrosivity of the binder without the inhibitor present, In one embodiment, these corrosion inhibitors can be utilized to decrease the corrosivity of the glass fiber-containing compositions described herein, Illustratively, corrosion inhibitors include one or more of the following, a dedusting oil or a monoamnonium phosphate, sodium merasilicate pentahydrate, melamine, tin(ll) oxalate, and/or methylhydrogen silicone fluid emulsion, When included in a binder of the present invention, corrosion inhibitors are typically present in the binder in the range from about 0,5 percent to about 2 percent by weight based upon the dissolved binder solids. One aspect of the present disclosure is that the need for corrosion inhibiting additives is greatly reduced by the alkalinity of the hinder solution and the substantially dehydrated uncured binder. In one embodiment, the binder is free from corrosion inhibitors and the corrosivity of the binder solution is within the acceptable range. [079] In illustrative embodiments, the binder may further include a non-aqueous moisturizer, The non-aqueous moisturizer may include one or more polycthers, For example, the non~ aqueous moisturizer may include an ethylene oxide or propylene oxide condensates having straight and/or branched chain alkyl and alkaryl groups. In one embodiment, the non-aqueous moisturizer includes a polyethylene glycol, a polypropylene glycol ether, a thioether, a polyoxyalkylene glycol (e.g. Jeffox TP400@), a dipropylene glycol, and/or a polypropylene glycol (e.g, Pluriol P425@ or Pluriol 2000@. In one embodiment, the non-aqueous moisturizer comprises a polyoxyalkylene glycol or a polypropylene glycol In another embodiment, the non-aqueous moisturizer includes a compound based on a polyhydroxy compound (eg., a partially or fully esterified polyhydroxy compound). In another etnbodiment, the non-aqueous moisturizer includes a polyhydroxy based on a glycerine, a propylene glycol, an ethylene glycol, a glycerine acetate, a sorbitol, a xylitol or a maltitol 10801 In another embodiment, the non-aqueous moisturizer includes other compounds having multiple hydroxyl groups based on tetrahydrofuran, a caprolActone, and/or alkylphenoxyp oly(ethyleneoxy)ethanols having alkyl groups containing from about 7 to about 1 8 carbon atoms and having from about 4 to about 240 ethyleneoxy units. For example, the non-aqueous moisturizer may include a heptylphenoxypoly(ethyleneoxy)ethanol and/or a nonylphenoxypolytethyleucoxylethanoJ, In another embhoditnent, the non-aqueous moisturizer includes a polyoxyalkylene derivative ofhexitol such as a sorbitan, sorbide, mannitan, and/or a mannide. In yet another embodiment, the non-aqueous moisurizer may include a partial long-chain fatty acids ester, such as a polyoxyalkylene derivative of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, and/or sorbitan trioleate, 10811 in i llustrative embodiments, the non-aqueous moisturizer includes a condensate of ethylene oxide with a hydrophobic base, the base being fomed by condensing propylene oxide with propylene glyclt In one embodimem, the non-aqueous moisturizer includes a sulfur containing condensate, such as those prepared by condensing ethylene oxide with a higher alkyl mercaptan (eg nonyl, dodeeyi, tetradecyl meaptan, or alkylthiophenols having about 6 to about 15 carbon atoms in the alkyl group) In another embodiment, the non-aqueous moisturizer includes an ethylene oxide derivative of a long-chain carboxylic acid, such as laurio, myristic, palmitic, or olcic acid, In yet another embodiment, the non-aqueous moisturizer includes an ethylene oxide derivative of a long-chain alcohol such as octyl, layl or cl alcohol. in another embodiment, the non-aqueous moisturizer includes an ethylene oxide/teltrahydrofuran copoyner or an ethylene oxide/propylene oxide eopolymer, [082] The following examples illustrate specific embodiments in further detail These examples are provided for illustrative purposes only and should not be construed as limiting the Invention or the inventive concept to any particular physical configuration in any way, EXAMPLES [083] Example 1: A solution of 50 g dextrose (0.278 mol), 50 g hexamethylenedianine (0.431 mol) dissolved in 566.6 g 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, 10841 Example 2: From the above solution of 50 g dextrose (0.228 mol), 50 g hexamethylenediamine (0.431 mnol) dissolved in 566.6 g deionized water (15% solids solution, pH 11 L9), 2g of the binder solution was applied on a filter pad which is played in a Moisture Balance and heated for 15 min at 120 0 C. A brownish water insoluble polymer formed on the filter pad. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8, [085J Example 3: A solution of 85 g dextrose (0.472 moB, 15 g hexamethylenediamine (0.129 mob dissolved in 566.6 g deionized water (15% solids solution, pH 10.8) was prepared. 2 g of the bhder solution was applied on a filer pad which is placed in a Moisture Balance and heated for' 1 minn at 140 4C. A brownish water insoluble polymer formed on the filter pad. An extraction of the cured fiter pad using 100 g of deionized water is essentially colorless and has a pi of 6. [086] Examole 4: A solution of 95 g dextrose (0.528 mob), 5 g hexamethylenediamine (0.043 mol) dissolved in 566.6 g deionized water (15% solids solution) was prepared. 2 g of the binder solution was applied on a filter pad which i placed in a Moisture Balance and heated for 15 min at 180 *C, A brownish water insolutble polymer formed on the filter pad. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8 [087] ComparativeExample 1; A solution of IN8 g dextrose (1 mob dissolved in 1020 g deionized water (15% solids solution) was prepared. 2 g of the binder solution was applied On a filter pad whe icis placed in a Moisture Balance and healed for 15 rmin a 180 *C. A water insoluble polymer was not termed on the filter pad. The resulting heat treated binder was essentially fuly water soluble. [0881 Cure Rate and Cre Time: Square Fiberglass mats (13" x 13") wihW6 weight of 44 g (corresponding to 34.5 g/ft) were impregnated with a binder containing 15% solids. Execss of binder is removed by vacuum suction, and the moist mat is dried for at least 12 hours at 90 "F in an oven (recirculati on). [0891 The dried mat is cut in four squares ofthe same dimension. The squares are stacked on top of each other, and at least one thermocouple connected to a recorder (i.e. oven mole) is placed in the middle of the stack between the 2'" and 3 layer, 10901 A mold press with temperature controlled platen is heated to 400 "F (204 *C). The sample with the prepared thermocouple is placed in the middle of the platen, and pressed to a thickness of 5/8" for a predefined time (i.e. 3,5 min, 4.0 min, 5.0 min, 6.0 nmn, 15 mit). [0911 Each molded sample was evaluated for the degree of cure by testing evenness of the surfaces, water hold-up, and extract. A sample was deemed to be cured when the surfaces are smooth without any "bumpsT the sample does not noticeably weaken when immersed in water, and no significant extract color is formed when inmersing the sample in water. The temperature profile of the center of the sample is measured during the molding cycle and is shown in Fi. 3. [0921 ,Comparative Example 2: Phenol Formaldehyde Binder. Composition based on dry solids; 2.41 parts Amim un Sufate 1.08 partof Anna 021 parts SilanA 101 9.3% phenol tormaldehydeaesin Urea Premix (70:30) Comparative Example 2 is referred to as Binder I within Fig. 3. [093) Comparative Example 3: Carbohydiratednoranic Acid Binder. Composition based on dry solds: HI 8159parts extrose 1709 Pars Am nim Sulfate 1 part of Ammonia 03 parts SiAMe Ai 0 omparie Eample 3 is referred to as Bind 2 in Fg. 3. [094) Example 5: Composition based ondry s litg - 80X94 parts Dextrose and Ammonia solution (an aqueous solution containing 2 mol/liter Dextrose and 2 mol/liter Ammonia) - 19.06 parts Hexamethylernediamine Example 5 is referred o as Binder 4 within Fig, 3, [095% It was determined that the time required to achieve full cure of a binder within the scope of the present disclosure is less than that of 3 comparative example binder systems baving diverse chemistries, This model system illustrates that the cure time, providing that other variables are kept constant, is dependent on the chemistry of the binder system. The chemistry of an illustrative binder composition within the scope of the present disclosure achieves improved cure times in comparison to these other exemplary systems, The results are shown following: Binder Molding Time to achieve full cure Comparative Ex. 2 -Binder_ I Minimum of 240 seconds Comparative Ex. 3 - Binder 2 Minimum of 300 seconds Ex, 5 - Binder 4 Cured at 210 second [0961 Referring now to Fig. 3, shown is the temperature profile characteristic for each of binders 1, 2, and 4. it was noted that the temperature profile is characteristic for each binder. It was not established that the cure rate and cure time is not characteristic of the cure temperature profile. However, the cura temperature profile helps to understand and predict cure rate and cure time. Specifically, Comparative Example 3 required the gr-eatest cure time and similarly the cure temperature profile required the greatest amount of time to asymptotically maximize. Similarly, Example 5 required the least amount of time to asymptotically maximize and demonstrated the shortest cure time. 109?J tCarbohydrate Reactant; Polvamine Raio Efeet on ure CvcM Time Wet Laid Mats (WL M) were made with varying ratios of dextrose monohydrate (DMH) to Hcxamethyiencdiarminc (HMDA). The weight ratios tested include 75/25, 85/15. and 92/8 respectively. 10981 A 15% Dextrose-HMDA Biudet was applied to 5 WLM's. The following binder compositions were prepared: Example 6 Exampke 7 Examle 8 DMH/HMDA 75/25 DM4HHMDA 85/15 DMFI/HMDA 92/8 Water 1677.45g 1677,45 g 1 6 77 ,45 g DMH1 246,78 a 2 79 .68 g 3 02.72 g HMDA 74.77 g 44,86 g 23,93 g Silane 1,00 gl100g 1,00 10991 The mats are prepared in 13"x13" pieces, with a thickness of 3/8". The press used to mold the mats is set at 4000F. Once the sample is molded it is approximately 5/8" thick, A temperature profile was first determined in a 15 minute interval, The next sample was pressed for 4 minutes; this is the time it takes to cure a complarable phenol formaldehyde binder composition (results not shw) he experiments were repeated with varying cure times until the minimum rime required to cure each composition was determined. The extent to which each binder had cured was determined based on weight. The following results were determined; Cre Cycle Tim Example 6nn, Example 7 4 min Example 8g miin [01001 As described above, comparable phenol formaldehyde based product (e.g, Comparative Example 2) cures with a 4 minute cycle time, Furthermore, a comparable carbohydrate based binder (eg. Comparative Exampie 3) cures with a 5 minute cycle time. These results indicate that a binder within the scope of the present disclosure with a carbohydrate reactant to primary polyamine of 85/15 or lower cures at a comparable or faster rate than the phenol formaldehyde based product, Further experiments showed that the cure temperature can be lowered in products having a shorter cure time to achieve equivalent cure times at lower temperatures, The results obtained agreed in principle to our expectations based on the Arrhenius equation. 101011 In addition to those examples described in detail, the following examples were made to ensure that the carbohydrate reactant and polyamine may comprise a wide range of alternates. Polyamine Carbohydrate Reactant Binder Formed 9 hexamethylenediamine dextrose Yes .10 etylenediamrine dextroeeYe diethylenetrianine dextrose Yes 12 hexamthylenediamine high futope corn syrup Ys 13 hexamethylenediamine scosYe S ctamethylenediaine tr Ys 15 tetramethyIenediamine dextrose Further Dextrose Nucleophie Eamples: [0102] Example 16: A suspension of 56.08 g deionized water, 7.15 g dextrose monohydrate, and 3.5 g 1,12-diaminododecane was acidified with 11 N HCI to pI 1., and heated to 70 !C under agitation resulting into a clear, colorless soluion. The solution forms a thermoset, water insoluble polymer at 160 *C, (Test condition: 2 g binder solution is applied on a filter pad which is placed in a Moisture Balance. The filter pad is heated for 15 min at 160 "C) An extract of the cured filter pad with 100 g of deionized water is essentially colorless, [01031 Eimule 17: A solution of 8.25g dextrose monobydrate. and 2.50 g 1,5-diamnino-2-methylpentne (Dytok A, Invista) dissolved in 56.08 a deionized water forms a thermoset water insoluble polymer at 160 "C, (Test condition: 2 g binder solution is applied on a filer pad which is placed in a Moisture Balance. The filter pad is heated for 15 nn at 160 *C. An extract of the cured filer pad with 100 g of demonized water is essentially colorless. [0104] Example 18: A solution of 8.03 g dextrose manohydrate, and 2.70 g N-(3-aminopropyl)-,3-propanediamnine dissolved in 56,08 g dcionzed water forms a thermoset, water insoluble polymer at 200 C. (Test condition: 2 g binder solution is applied on a filter pad which is placed in a Moisture Balance, The filcr pad is heated for 15 mn at 200 *C.) An extract of the cured filter pad with 100 g of deionized water has a slight yellowish color. [01051 Example 19: A solution of 3 g dextrose (0,016 mol and 0.5 g examethylenediamine (0.004 mol) dissolved in 9 mL deionized water was prepared. This reaction mixture was heated at 100 Cc for I hour before 0,7 g of dithiothreitol (0.004 mwo) was added to the mixture which was dropped on a filter pad, this filter pad was heated at 125 4C, A brownish water insoluble polymer was formed on the filter pad. [0106] Example 20: A solution of 3 g dextrose (0.016 mo), 0.5 g hexamcthylenediainc (0,004 mo) dissolved in 9 M' deionized water was prepared. This reaction mixture was heated at 100 "C for I hour before 0.52 g of butanedithiol (0.004 mol) was added to the mixture which was dropped on a filter pad, this filter pad was heated at 125 "C. A brownish water insoluble polymer was formed on the fi'e pad. I 01071 Procedure for andyzing a bnder saem le with oasp nrois Approxinmtely 10 g of a cured product having the binder thereon is placed in a test tube, which tube is then heated to 1000 "F for 2.5 minutes at which time the headspace is sampled and analyzed by gas chromatography/mass spetronetry (GC/MS) under the following conditions: Oven, 50 *C for one minute -10 'C/minue to 300 C for 10 minutes; Inlet, 280 *C splitless; Column, HP-S 30 um x 0.32 mm x 0.25 um: Coumn flow, 1.11 L/minOte Helium; Detector, MSD 280 *C; Injection volume, I ml; Detector mode, scan 34-700 amu; Threshold, 50; and Sampling Rate, 22 scans/second, A computer search of the nass spectrum of a chromatogaphic peak in the sample is made against the Wiley library of mass spectra. The best match is rep orted A quality index (closeness of match to the library spectra) ranging fron 0 to 99 is generated, Only the identity of peaHks with a quality index of greater than or equal to 90 is reported. [01081 The following table provides representative pyrolysis data that one expects from the GC/MS analysis of gaseous compounds produced during pyrolysis of a melanoidin based binder composition; Retention Time (mi Tentative Identification 1 Peak Area 1.15 2-cyclopenten- -On 10.67 1-34 2,5-dinmethyl-fliran 5.84 3.54 futran 2.15 3.60 3-methyl-2,5-furandione 3.93 4,0 phenol 0.38 4.89 2,3-dimethyl-2-cycopenten -1one 1.24 5.11 2-methyl phenol 1 19 5 A2 4-methyl phenol 2.17 6.46 2,4-dimethyl-phenol 1. 13 10.57 dimethylphthalate 0.97 17,89 octadecanoic acid L.0 22.75 rucylamide 9.72 [0109] Following is a listing of the species observed in the pyrolysis gas chromatography mass spectrometry (Py GC-MS) of a binder sample prepared using hexamethylenediamine as the polyamine component. The pyrolysis was carried out at 200 0 C, 300 C, and 770 "C. Fingerprinting shows a very significant peak which corresponds to acetic acic in the mass chromatograN at both 200 "C and 300 "C which was not seen in a sample made using dextrose and ammonium sulfate ( )etCoparativc Example 31, in which the significant volatile was $02, particularly at 300 "C. At 770 "C, the peaks observed, in order of increasing retention lime were assigned as follows: A: Co-elating CS 1

HI

0 , C 5

H

12 , acetone, possibly low mw acetic avid ester; B: C 5 Hgdiene;C C: 5 Hg diene; D: likely a pentanol; E: C611 12 - a methyl penene; F: hexane; G: methylcyclopentane; -: a cyclohexadiene; 1: C6H110 - probably a methylcycJopetane; J: benzene; K: acetic acid; L: cyclo ne; M: probably nonanol; N: 2-methy1-3-pentanone; 0: 2,5-dinethylfuran; P: C7Hig1+ unassigned co-elate; Q: pyridine + unassigned co-elute; R: toluene; 5: possibly decenal + unassigned co-elute; T: 2-ethyl-5-methyifuran; U: a methyl pyridine; V: a methyl pyrrele: W: a xylene; X: unassigned - with alcohol functionality; Y: unassigned; Z: a xylene + unassigned co-elate; AA: unassigned; AB: a dimethyl pyrrole; AC: a dimnethyl pyridine; AD: a dimnethyl pyridine; Al: unassigned: AF: unassigned; AG: an ethyl methyl pyrrole +unassigned co-elote; AT: an unassigned but distinct mass spectrum (N-containing), pyr'ole related: AJ: an unassigned but distinct mass spectrum (N-containing), possibly an acetanide; AK: an assigned but distinct mass spectrum (N-containing), pyrrole related; AL: an unassigned hut distinct mass spectrum (N-containing), pyrrole related; AM: an unassigned but distinct mass spectrum Ncontaining), pyrrole related,. The distinct mass spectra seen from peaks Al to AM are not seen in the data of prior binders not having the polyaminco component. [O110j Procedure forLealuauAat dad wa teed ensile an ed. When evaluat ed for their dry and "weathered" tensile strength, glass bead-containing shell bone compositions prepared with a given bmder provide an indication of the likely tensile strength and the likely durability, respectively. of a fiberglass product prepared with that particular binder. Predicted durability is based 30 on a shell bone's weathered tensile strength dry tensile strength ratio, Shell bones are prepared, weathered, and tested as follows, for example, for a hexamethylenediamine-dextrose binder mixture. [01IJ il lA shell bone mold (Dietert Foundry Testing Equipment; Heated Shell Curing Accessory, Model 366, and Shell Mold Accessory) is set to a desired temperature, generally 425 1, and allowed to heat up for at least one hour, While the shell bone mold is heating, approximately 100 g of an aqueous binder generaly 15% in binder solids) is prepared (e.g. as described in Example 7). Using a largo glass beaker, 727,5 g of giass beads (Quality Ballotini impact Beads, Spec. AD, US Sieve 70 140, 106-212 mnicron47, from Potters Industries, Inc.) are weighed by difference. The glass beads are poured into a clean and dry mixing bowl, which bowl was mounted onto an electric mixer stand. Approximately 75 g of aqueous binder is poured slowly into the glass beads in the mixing bowl The electric mixer is then turned on and the glass beads! hinder mixture is agitated for one minute. Using a large spatula, the sides of the whisk (mixer) are scraped to remove any clumps of binder, while also scraping the edges wherein the glass beads lay in the bottom of the bowl The mixer is then turned back on for an additional minute, and then the whisk (mixer) is removed front the unit, followed by removal of the mixing bowl containing the glass beads/binder mixture. Using a large spatula, as much of the binder and glass beads attached to the whisk (mixer) as possible are removed and then stirred into the glass beads/hinder mixture in the mtixing bowl, The sides of the bowl are then scraped to mix in any excess binder that might have accumnulatd on the sides, At this poAit, the glass beads/hexamothylenediamini-extrose binder mixture is ready for molding in a shell bone mold, [11] The slides of the shell bone mold are confirmed to be aligned within the bottom mold platen. Using a large spatula, a glass beadshexamethylenediamine-dextrose binder mixture is then quickly added into the three mold cavities within the shell bone mold. The surface of the mixture in each cavity is flattened out, while scraping off the excess mixture to give a uniform surface area to the shell hone, Any inconsistencies or gaps tha existed in any of the cavities are filled in with additional glass beads/hexamethylenediamine-dexrose binder mixture and then flattened out One a glass beads/hexamethyleneiamnine-dextrose binder mixture is placed into the shell bone cavities, and the mixture is exposed to heat, curing begins. As manipulation time can affect lest results, eg, shell bones with two differentially cured layers can be produced; shell bones are prepared consistently and rapidly, With the shell bone mold filed, the top platen is quickly placed onto the bottom platen, At the sane time, or quickly thereafter, measurement of curing time is initiated by means of a stopwatch, during which curing the temperature of the bottom platen ranged from about 400 to about 430 T, while the temperature of the top platen ranged from about 440 T to about 470 . At seven minutes elapsed time, tihe top platen is removed and the slides pulled out so that all three shell bones can be removed, The freshly made shell hones are then placed on a wire rack, adjacent to the shell bone mold platen, and allowed to cool to room temperature, Thereafter, each shell bone is labeled and placed individually in a plastic storage bag labeled appropriately, If shell bones can not be rested on the day they were prepared, the shell bon-oraiNng plastic bags were placed in a desiccator unit. 0113j Condirionin (Weatherin) Procedurer- Shelf Rone: A Blue M1 humidity chamber is tuned on and then set to provide weathering conditions of 90 0 "F and 90% relative humidity (i.e., 90F /90% rHV The water tank on the side of the humidity chamber is checked and filled regularly, usually each time it is turned on. The humidity chamber is allowed to reach the specified weathering conditions over a period of at least 4 hours, with a day-long equilibration period being typical Shell bones to be weathered are loaded quickly (since while the doors are open both the humidity and the temperature decrease, one at a time through the open humidity chamber doors onto the upper, slotted shelf of the humidity chamber. The time that the shell bones are placed in the humidity chamber is noted, and weathering is conducted for a period of 24 hours. Thereafter, the humidity chamber doors are opened and one set of shell bones at a time are quickly removed and placed individually into respective plastic stoe bags, being sealed completely. Generally, one to four sets of shell bones at a time are weathered as described above. Weathered shell bones are immediately taken to the Instron room and tested. !0114] Ter Procedure4 Breakin S hell Bones: in the Instron room, the shell hone test method is loaded on the 5500 .R Instron machine while ensuring that the proper load cell is installed (i.e., Static Load Cell 5 kN), and the machine is allowed to warm up for fifteen minutes. During this period of time, shell hone testing grips are verified as being installed on the machine. The load cell is zeroed and balanced, and then one set of shell bones is tested at a time as follows: A shell bone is removed from its plastic storage bag and then weighed, The weight (in grams) is then entered into the computer associated with the instron machine. The measured thickness of the shell bone (in inches) is then entered, as specimen thickness, three times into the computer associated with the Instron machine. A shell bone specimen is then placed into the grips on the Instron machine, and testing initiated via the keypad on the Instron machine. After removing a shell bone specimen, the measured breaking point is entered into the computer associated with the instron machine, and testing continued until all shell bones in a set are tested. [011i5\ Carbohydatew Reactant; Povamine R~atio Eect on Shell Bone roerties. Shell Bones were made with varymg ratios of dextrose monohydrate (DMH1) to Hexaethylenediamine (IMDA) with a silane additive (O0200) were examined as described above, at a test speed of 25 mm/vmin. The weight ratios tested include 90/10, 85/I5, 80/20 and 75/25, respectively.

Str ngth Stress at peak / MNm^r 2 Ls Dry Weathered 90% DM H+ 10% H MDA+ 0.3% 1510200, p H 11 .06 2,954 1L929 34.9 85% DMH+± 15% HMDA+ (.

3 % TS102004 pH 129 2,573 2,017 21 80% DMH+k 20% HMDA4 03% 1S10200 pH 11.54 2.747 2,344 1468 75% DMH+ 25% HMDA+ 0.3% iS 10200. pH- 1 1.71 2.735 2,073 24.2 Example: Glass Wool (Fiber Gh) Tri [0116j Comparisons of the qualities of two glucose-- hexamethylenediamine hinders with a standard binder in terms of curing and rigidity on a glass wool product (Ae+032 100 mm 1200 mm width; 32 kg/m 3 - 15 m/min) were carried out by measuring the parting strength and density, Binder 1: 85% glucose 15% hexamethylenediamine. Binder 2: 90% glucose -10% hexamothylenediamine. [0117J Ordinary Parting Strength (Before Autoclave) and Weathered Parting Strength (After Autoclave) may be measured as described in International Patent Application. Publication Number WO 2008/089851 or W02009/019235 Parting strengtho a 4atndard binder: )REJ3 ACTUGCLAVE" _AFTER AUOCLAVE We h () urv N)dnsit (gnfl eig I Forte (N) density (k 'i 2 ------------ ---- - - - -22 0 1>20-- 7't[ -~ 9-19.0--------->' P S, BEFOL g9. fu~ .. FE 3. fw Partig strength on Birxder1 WePtg Fit()density(r)Weih~)Iu~ lnit ka' 220 N4 001Vt\ M 7T 19.80m 4 1 8.1 : - -|5 A 1 02 .5 --- L 3.0 ~ " " ~ '' - ~ ~ ' ' 2 1 .0 A Ngf Tota MN : j 13A aa 3061.5 26,6 419266 i50632.0 g P.S BEFORE; 360,8 ggwi P.S AFTER : 271.3 grg LOSS 89,3 gf/e i e 24.8 Parting strength on inder 2: M.OE AUTOCLAV.,E Afr.R AUTOCLAVE

-

F ( et ( Wihi Force (N) density kg/mi) OS__ 1 g!.2t 0 193 Observations durng the trial: The product was browner on the linewith the two alucosen hexametihylenediamine binders, 101 18J Conclusions: With the two glucose-- hexamnethylenediiamine binders , the parting strength (which is a longitudinal tensile strength) results showed a significant improvement; and a significant improvement was observed in three other rigidity tests ("60'" test - sagging measured when leaned at 604 against a chute: "table" test -sagging measured against a horizontal plane; and Acermni test sagging measured 35 cm from the edge of a table). Example: Particle Board Trial [01191 Comparisons of the qualities of particle boards made using a urea-formaldehyde binder (UF E0) and using a carbohydrat e polyarmine (hexamethylcefedanmine} binder were carried out under the following conditions. Board size: 350 x 333 mm and mainly 1 0 mmn thick (2K20mm), Platen temperature: 195 "C mainly but also, 175 and -215 *C. Pressure: 3,5 Mpa (35 bar) Quoted - Actual 35 Kg/cm 2 , 56 bar to achieve. Density target: 650 kg/mr 3 Pre-formn prepared prior to pressing Results; Binder 3 PressTime | lB Strength 1 U? hO(secs) (Mpa) UE E0 |__ 150 0.75 .100 0.69 Carbohydrate 8066 polyamnine 300 0,92 ________ 240 0.99 ________ 150 0.73 ______12 0 [ 0.68 _______910 0,(X5 All boards prepared appeared of igh quality; no splits or degassing were observed, The boards made with this carbohydrate polyamine formulation match urea formaldehyde board when they are cured for 1 50 seconds,

Claims (37)

1. 2. The binder of claim 1, the carbohydrate reactant is a polysaccharide.
2. 3. The binder of claim 1, wherein the carbohydrate reactant is a monosaccharide or a disaccharide. ,4 The binder of claim 1, wherein the carbohydrate reactant is a monosaccharide in its aldose or ketose form.
3. 5. The binder of claim 1, wherei the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtres thereof
4. 6. The binder of any one of cains 1-5, wherein R 1 and R 2 form covalent bonds with the carbohydrate reactant to form the polymerlic product. 7, The binder of any one of Oaims 16, wherein Rl is a nucleophilic moiety and R2 is a stabilization moiety. 8, The binder of any one of claims 1-7, wherein Q is an aiky! selected from the group consisting of C2-C24
5. 9. The binder of any one of claims 1-7, wherein Q is an aMkyI selected from the group consisting of C2-C.
6. 10. The binder of any one of claims -7, wherein Q is an alkyl selected from the group consisting of C-C 7 .
7. 11. The binder of any one of claims i-7, wherein Q is a C 6 ayl
8. 12. The binder of any one of claims 1- wherein Q is selected from the group consisting of a cycloheyi cyclopentyl or vclobutyl.
9. 13. The binder of any one of claims 1-7, wherein Q is a benzyl. 14, The binder of any one of claims 1-7 wherein R -Q-R 2 is 2-((2-amninoethyllamnino] ethanol -36
10. 15. The binder of any one of claims 1-13. wherein each of RI and R 2 is thiol.
11. 16. The binder of any one of claims 1-13, wherein R i is an amine,
12. 17. The binder of claim 16, wherein R 2 is an amine, an aide, an imin , or an
13. 18. The binder of claim 16, wherein R2 is an amine.
14. 19. The binder of any one of claims 1- 18, wherein a mole ratio of the carbohydrate rectan to he neoph is in terane ofaout 1:1 to about30: 20 The bnr of any one oflims O S when a moe ratioof e carbohydrate reactant to the nucleophe is in the range ofabout2:to about 11
15. 21. The Ideof any one ims 1 herein an aueous extractof the polymeric product has a pH inA he rangelof about 5 to about 9
16. 22. The binder of any one of claims 1-2 whrein an aqueous extract of the polymericoductisessentil les
17. 23. The binder any one o cais 122 herein an aqeos trat o the piymeric product is a capable of redCcing Benedic' agent.
18. 24. The binde of any one of caims 23, wherein the polymeric product is phenol ice andonadchyde-frec 25 Thebnder of any one of cims 1-24, wherein the carbohydrate reactant and the n uleophile are non- vlaie.
19. 26. The binder of any one of claims 1-25, wherein a oun in cont c h the binder reduces Benedicts reagent.
20. 27. The binder of any one of claims 1-26, wherein the polymeric product strongly absorbs light at 420 m. 2E. A method of making a collecon of mater bound wi a polymeric binde compring: prparing a sohton contaiing reactuts fo pradung he poymeri bdind and a solvent wherein the reans incld a cabohydrate reactant and a nuceophile disposng the solution onto the collction of matter; volilizing the solvent to form anuncured product, and subjecting the uneured product to conditions that cause the carbohydrate reactant and thenoophile topolymerize to m the polymeric binder. The medithod of caim 28, wheeinthe election of matercopriss t collection of matr includes bers selectrnt thegoup consisting of mineral fbers, aramid fibers, ceramic fibers metl bers, carbon fibers polyimide bers, polyester fiber, rayon be, and celulosi fibers
21. 30. The method of clivm 28,wherein thecollecton ofmatter glass fibers
22. 31. The method of claim 30, wherein the glass fibers arc present in the range from about 70% to about 99% by Weight.
23. 32. The method of claim 28, wherein the collection of matter comprises celiulosie afibern.
24. 33. The method of claim 32, wherein the cellulosic fibers are substrate selected from the group consisting of wood shavings, sawdust, wood pulp and ground wood,
25. 34. The method of claim 28, further comprising packaging the uncured product in a packaging material suitable for storage.
26. 35. The method of claim 28, wherein preparing the solution inchides adding an amount ofthe carbohydrate reactant and an amount of the nucleophile so a weight ratio is in the range of about 2:1 to about 10:1.
27. 36. The method of claim 28, wherein preparing the solution includes adding the carbohydrate reactant and The nucleophile to an aqueous solution. 37, The method of claim 36, wherein preparing the solution includes adjusting the pH of the solution to within the range of about 8 to about 12. 38, A composition comprising a collection of matter and a binder, the binder compnsing polymeric products of a reaction between a carbohydrate reactant and a nucleophile, the polymeric products being substantially water insoluble.
28. 39. The composition of claim 38, wherein the collection of mater includes fibers selected from the group consisting of mineral fibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, and cellulosic fibers.
29. 40. The composition of clain 38, wherein the collection of matter includes glass fibers.
30. 41. The composition of claim 38, wherein the collection of matter includes cellulosic fibers,
31. 42. The composition of claim 41, whetein the cellulosic fibers arc present in a cellulosic substrate selected from the group consisting of wood sharing, sawdust, wood pulp, ground wood jute, flax, hemp, and straw.
32. 43. The composition of any one of claims 3842, wherein the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose. dihydroxyacetone, and mixtures thereof.
33. 44. The composition of ay one of claims 38-43, wherein the nucleophile is a compound having a nucleophilic moiety and a stabilization moiety
34. 45. The bindeS of any one of claims 38-44, wherein the nucleophile is R 1 -Q-R , wherein A-38 (a Q is aWT cyclolkyl roalkyl oryloeteayl each of which is optionally R is theninckophili moiety, and (c) R2 is the stabilization moiety.
35. 46. The composition of any one of claims 38-45 further comprising a silicom contaming compound, 47, The compositin of aim 46, whern he sil con-conaing compounds selected from the group consisting of gamma-aminopropy ltrieftoxysilane, gammna glycidoxypropyftrimecthoxysilane, amincertylaminopropyltrimiethoxysilane, an aninoofumnctional oligomerc siloxane, and mixtures Thereof
36. 48. The composition of claim 46. wherein the silicon-comaining compound is ganmna-aminopropyltrietboxysilane,
37. 49. The composition of any one of claims 38-48, either comprising a corrosion inhibitor selected from the group consisting of deducting oil, monoammonium phosphate, sodium metasilicate penlahydrate, melaminc, tin (II)oxalate, and a mnethylhydrogen silicone fluid emulsion.