US 2015.0017856A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0017856A1 DAVIS et al. (43) Pub. Date: Jan. 15, 2015

(54) ARTICLE INCLUDING INTUMESCENT Publication Classification COATING, PROCESS FOR FORMING AND USE OF SAME (51) Int. Cl. C09D 5/18 (2006.01) (71) Applicant: NATIONAL INSTITUTE OF (52) U.S. Cl. STANDARDS AND TECHNOLOGY, CPC ...... C09D 5/185 (2013.01) GAITHERSBURG, MD (US) USPC ...... 442/138; 428/331; 428/319.3; 428/328; 252/606 (72) Inventors: RICK DOWELL, DAVIS, (57) ABSTRACT IJAMSVILLE, MD (US); YU-CHIN LI, An article includes a Substrate and an intumescent coating to WASHINGTON (TW) form an intumescent product in response to heating the article. The intumescent coating is disposed on the Substrate (21) Appl. No.: 14/497,951 and includes a primary intumescent precursor and a layered material that includes a silicate mineral, a layered double hydroxide, or a combination thereof. The primary intumes (22) Filed: Sep. 26, 2014 cent precursor includes a carbohydrate polymer. A process for forming an article includes forming a liquid composition by disposing in a solvent a primary intumescent precursor and a Related U.S. Application Data layered material, contacting a Substrate with the liquid com (60) Provisional application No. 62/033,780, filed on Aug. position, and forming an intumescent coating on the Substrate 6, 2014. to form the article.

Patent Application Publication Jan. 15, 2015 Sheet 1 of 5 US 201S/0017856 A1

2

FIG

FIG 2 Patent Application Publication Jan. 15, 2015 Sheet 2 of 5 US 201S/0017856 A1

FIG 3

FIG, 4 Patent Application Publication Jan. 15, 2015 Sheet 3 of 5 US 201S/0017856 A1

Patent Application Publication Jan. 15, 2015 Sheet 4 of 5 US 201S/0017856 A1

A 6OO Comparative Foam 500 - intumescent Coated Foam 4OO A: PHRR of 580 kW/m2 at 132S, THR of 121 MJ/m2, AHRR of 63 kW/m2 3OO B: PHRR of 113 kW/m2 at 199S THR of 50 MJ/m2, AHRR of 21 kW/m2 2OO PHRR: peak heat release rate B THR: total heat release

AHRR: average heat release rate 1OO

FG, 6 Patent Application Publication Jan. 15, 2015 Sheet 5 of 5 US 201S/0017856 A1

Comparative Foam 50 - Average Mass Loss = 43.7%

3: ...... :-:- 3%. Starch -11.5% SPB - 2% MMT Coated foam 58 Average Mass loss = 6.7%

3.

3- c) i:divisis:siindividual tessites:s rrr & 3AYeage

O 30 30 fest its rations asia)

F.G. 8 US 2015/001785.6 A1 Jan. 15, 2015

ARTICLE INCLUDING INTUMESCENT BRIEF DESCRIPTION OF THE DRAWINGS COATING, PROCESS FOR FORMING AND 0008. The following descriptions should not be consid USE OF SAME ered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike: CROSS REFERENCE TO RELATED 0009 FIG. 1 shows a cross-section of an article: APPLICATIONS 0010 FIG. 2 shows a cross-section of an article: 0011 FIG.3 shows a micrograph of an article according to 0001. This application claims the benefit of U.S. Provi Example 1: sional Patent Application Ser. No. 62/033,780 filed Aug. 6, 0012 FIG. 4 shows a higher magnification micrograph of 2014, the disclosure of which is incorporated herein by ref the article shown in FIG. 3; erence in its entirety. 0013 FIG. 5 shows a graph of intensity versus energy obtained from Energy-dispersive X-ray spectroscopy STATEMENT REGARDING FEDERALLY (EDEX) of the article according to Example 1: SPONSORED RESEARCH 0014 FIG. 6 shows a graph of heat release rate (HRR) Versus time for the article according to Example 1: 0002 This invention was made with United States govern 0015 FIG. 7 shows a graph of total mass loss versus test ment support from the National Institute of Standards and duration for a comparative foam according to Example 2; and Technology. The government has certain rights in the inven 0016 FIG. 8 shows a graph of total mass loss versus test tion. duration for the article according to Example 1.

BACKGROUND DETAILED DESCRIPTION 0017. A detailed description of one or more embodiments 0003 Reduction in flammability of consumer goods has is presented herein by way of exemplification and not limita occurred over the past century. However, certain residential tion. upholstered furniture is implicated in a high proportion of fire 0018. It has been found that article that includes an intu losses due to its flammability that plays a role in rapid fire mescent coating that includes a carbohydrate polymer and a growth that leads to flashover. Flashover is a condition that layered material disposed on a Substrate and formed, e.g., by results in spontaneous ignition of objects proximate to a burn dipping the substrate into a liquid composition has a substan ing item. tially reduced flammability with respect to the substrate with 0004. Accordingly, articles and processes for mitigating out the intumescent coating. flammability would be well received in the art. 0019. According to an embodiment, an intumescent coat ing responds to presence of heat to produce an incombustible BRIEF DESCRIPTION residue referred to as char that expands and forms an incom bustible foam that has fire insulation properties. The intumes 0005. The above and other deficiencies are overcome by, cent coating includes a carbon Source, an acid source, and a in an embodiment, an article comprising: a Substrate; and an blowing agent. Without wishing to be bound by theory, it is intumescent coating to form an intumescent product in believed that the acid, in response to being heated, catalyzes response to heating the article, the intumescent coating being dehydration of the carbon source, and the carbon Source is disposed on the Substrate and comprising: a primary intumes converted to a carbon char. The blowing agent releases a cent precursor comprising a carbohydrate polymer, and a nonflammable gas in response to being heated, and the non layered material comprising a silicate mineral, a layered flammable gas contributes to forming the incombustible double hydroxide, or a combination comprising at least one of foam. Accordingly, components of the intumescent coating the foregoing. form an intumescent product (e.g., the incombustible char and incombustible foam) when heated to a temperature that is 0006 Further disclosed is a composition comprising: a greater than or equal to a temperature for activating the acid Solvent; a primary intumescent precursor to contact a Sub Source to catalyze formation of char from the carbon Source. strate and to form an intumescent coating on the Substrate, the 0020. According to an embodiment, as shown in FIG. 1, primary intumescent precursor being disposed in the Solvent article 2 includes intumescent coating 4 disposed on Substrate and comprising a carbohydrate polymer, and a layered mate 6. Intumescent coating 4 includes primary intumescent pre rial to be dispersed among the primary intumescent precursor cursor 8 and layered material 10. Intumescent coating 4 forms in the intumescent coating on the Substrate, the layered mate an intumescent product in response to heating article 2. rial being disposed in the solvent and comprising a silicate 0021. In an embodiment, as shown in FIG. 2, article 2 mineral, a layered double hydroxide, or a combination com includes intumescent coating 4 disposed on Substrate 6. Intu prising at least one of the foregoing. mescent coating 4 includes primary intumescent precursor 8. 0007 Additionally disclosed is a process for forming an layered material 10, and secondary intumescent precursor 20. article, the process comprising: forming a liquid composition Intumescent coating 4 forms an intumescent product in by: disposing in a solvent a primary intumescent precursor response to heating article 2. comprising a carbohydrate polymer, and disposing in the 0022. In some embodiments, intumescent coating 4 Solvent a layered material comprising a silicate mineral, a includes an additive. layered double hydroxide, or a combination comprising at 0023. According to an embodiment, primary intumescent least one of the foregoing; contacting a substrate with the precursor 8 includes a carbohydrate polymer, and layered liquid composition; and forming an intumescent coating on material 10 includes a silicate mineral, layered double the substrate to form the article. hydroxide, or a combination thereof. US 2015/001785.6 A1 Jan. 15, 2015

0024 Substrate 6 includes a polymer, textile, metal, glass, cell, closed cell, or combination thereof. In an embodiment, ceramic, or a combination thereof. the polymer is a foam that includes polyurethane having open 0025. In an embodiment, substrate 6 includes the polymer, cell to exhibit fluid permeability therethrough. and the polymer is a thermoset, thermoplastic, or a combina 0029. In an embodiment, substrate 6 includes the textile. tion thereof. A “thermoset polymer solidifies when first The textile refers to a woven or non-woven material that heated under pressure and thereafter may not melt or mold includes a network of a plurality of fibers. Textiles can be without destroying original characteristics of the thermoset made directly from fibers or a web of fibers or from yarn polymer. Thermosetting polymeric materials include comprising a plurality of fibers. Textiles include clothes and epoxides, phenolics, melamines, ureas, polyurethanes, pol fabrics. The fibers can be a material characterized as an ani ysiloxanes, or polymers including a suitable cross-linkable mal material (e.g., wool, silk, and the like), plant material functional moiety. (e.g., cotton, flax, jute, bamboo, and the like), mineral mate 0026. A thermoplastic polymer has a macromolecular rial (e.g., asbestos, glass fiber, and the like), synthetic material structure that repeatedly softens when heated and hardens (e.g., nylon, polyamide, polyester, and acrylic), and the like. when cooled. Illustrative examples of thermoplastic poly The textile can be a non-mineral material such that the textile meric materials include olefin-derived polymers, e.g., poly contains less than or equal to 10 weight-percent (wt %), ethylene, polypropylene, and their copolymers; polymethyl specifically 5 wt % or less, more specifically 1 wt % or less, pentane-derived polymers, e.g., polybutadiene, polyisoprene, and further specifically 0 wt % mineral fibers, based on a total and their copolymers; polymers of unsaturated carboxylic weight of the textile. acids and their functional derivatives, e.g., acrylic polymers 0030. According to an embodiment, the textile is drapable. Such as poly(alkyl acrylates), poly(alkyl methacrylate), poly As used herein, “drapable” means that the textile is foldable acrylamides, polyacrylonitrile, and polyacrylic acid; alkeny (i.e., capable of folding) over an object, hanging loosely laromatic polymers, e.g., polystyrene, poly-alpha-methylsty under the textile's own weight, or shapably conformable to rene, polyvinyltoluene, and rubber-modified polystyrenes; substrate 6. A drapable textile can be used for clothing, uphol polyamides, e.g., nylon-6, nylon-66, nylon-11, and nylon-12; stery, window drapes, curtains, and the like. In certain polyesters, such as, poly(alkylenedicarboxylates), including embodiments, e.g., the textile is non-drapable, i.e., not drap poly(ethylene terephthalate) (PET), poly(1,4-butylene able. terephthalate) (PBT), poly(trimethylene terephthalate) 0031. In some embodiments, the textile includes fibers (PTT), poly(ethylene naphthalate) (PEN), poly(butylene Such as an animal or plant fiber. Such textiles can be a natural naphthalate) (PBN), poly(cyclohexanedimethanol terephtha textile since the textile is made of fibers from a naturally late), poly(cyclohexanedimethanol-co-ethylene terephtha occurring material. In an embodiment, a natural textile has a late) (PETG), and poly(1,4-cyclohexanedimethyl-1,4-cyclo different burning characteristic than a synthetic material. It is hexanedicarboxylate) (PCCD), and poly(alkylene contemplated that a synthetic material can melt due to heat, arenedioates); polycarbonates; co-polycarbonates; co-poly e.g., from a flame, rather than char or combust. It also is estercarbonates; polysulfones; polyimides; polyarylene Sul contemplated that natural material can burn or char rather fides; polysulfide Sulfones; and polyethers such as pol than melt. yarylene ethers, polyphenylene ethers, polyetherSulfones, 0032. According to an embodiment, the textile is tear, polyetherimides, polyetherketones, polyetheretherketones; heat, abrasion resistant material Such as aramid fibers or or blends or copolymers thereof. polybenzamidazole fibers. Commercially available aramid 0027. Examples of the polymer include polyurethanes, materials include NOMEX and KEVLAR (both trademarks epoxies, ethylene propylene diene rubber (EPR), ethylene of E.I. DuPont de Nemours & Co., Inc. of Wilmington, Del.), propylene diene monomer rubber (EPDM), melamines, poly and commercially available polybenzamidazole fibers acetals, polyacrylamides, polyacrylics such as polyacrylic include PBI fibers (a trademark of PBI Performance Fabrics acid, polyacrylonitriles, polyamides, including polyamide of Charlotte, N.C.). Thus, the textile can be an aramid mate imide, polyarylene ethers, polyarylene Sulfides, polyarylene rial, a blend of aramid materials, a polybenzamidazole mate Sulfones, polybenzoxazoles, polybenzothiazole, polybuta rial, a blend of aramid and polybenzamidazole materials, or dienes and copolymers thereof, polycarbonates, polycarbon other material such as BASOFIL (trade name material avail ate esters, polyether ketones, polyether ether ketones, poly able from Basofil Fibers, LLC of Enka, N.C.), ZYLON (trade ether ketone ketones, polyetherSulfones, polyesters, name material available form Toyo Boseki Babushiki Kaisha polyimides such as polyetherimides, polyisoprenes and of Osaka, Japan), and the like. copolymers thereof, polyolefins such a polyethylene and 0033. The textile can exhibit resistance to absorption of copolymers thereof, polypropylene and copolymers thereof, water or other moisture and can include a water repellent and polytetrafluoroethylene, polyphosphaZenes, poly(alkyl) material Such as a polymer, e.g., a perfluorohydrocarbon Such (meth)acrylates, polystyrenes and copolymers thereof, rub as TEFLON (trade name material available from E.I. Du Pont ber-modified polystyrenes such as acrylonitrile-butadiene de Nemours and Company of Wilmington, Del.), polytet styrene (ABS), styrene-ethylene-butadiene (SEB), and rafluoroethylene (PTFE) such as GORE-TEXCROSSTECH, methyl methacrylate-butadiene-styrene (MBS), polyoxadia or CHEMPAK materials (all three of which are trademarks of Zoles, polysilaZanes, polysulfones, polysulfonamides, poly WI. Gore & Associates, Inc. of Newark, Del.), polyurethane vinyl acetates, polyvinyl chlorides, polyvinyl esters, polyvi based materials, neoprene-based materials, cross-linked nyl ethers, polyvinyl halides, polyvinyl nitriles, polyvinyl polymers, polyamide, and the like. thioethers, polyureas, polyurethanes, and silicones. A com 0034. In an embodiment, substrate 6 includes the metal. bination comprising at least one of the foregoing polymers Exemplary metals include a metal from the periodic table or can be used. In an embodiment, the polymer is polyurethane. an alloy of a plurality of metals from the periodic table. 0028. According to an embodiment, substrate 6 is the Metals include, for example, magnesium, aluminum, tita polymer, and the polymer comprises a foam. The film is open nium, manganese, iron, cobalt, nickel, copper, molybdenum, US 2015/001785.6 A1 Jan. 15, 2015 tungsten, palladium, chromium, ruthenium, gold, silver, Zinc, 0039. In an embodiment, primary intumescent precursor 8 Zirconium, Vanadium, silicon, or a combination thereof, includes the carbohydrate polymer, which is a polysaccha including alloys thereof. Particularly, the metal can be an ride, nucleic acid, or a combination thereof. The polysaccha aluminum-based alloy, magnesium-based alloy, tungsten ride includes a plurality of Sugar monomers. The nucleic acid based alloy, cobalt-based alloy, iron-based alloy, nickel includes a plurality of Sugar monomers and nucleobase based alloy, cobalt and nickel-based alloy, iron and nickel OOCS. based alloy, iron and cobalt-based alloy, copper-based alloy, 0040. In an embodiment, the polysaccharide is formed from two or more monosaccharides joined by glycosidic and titanium-based alloy. As used herein, the term “metal bonds. Polysaccharides formed from 3-10 monosaccharides based alloy’ means a metal alloy wherein the weight percent can be referred to as oligosaccharides. According to an age of the specified metal in the alloy is greater than the embodiment, the carbohydrate polymer includes a Sugar weight percentage of any other component of the alloy, based monomer Such as a Sugarfuranosyl ring or a pyranosyl ring), on the total weight of the alloy. a modified Sugar, an acyclic group (e.g., an acyclic ether, an 0035. In an embodiment, substrate 6 includes the glass. acyclic mercaptan, an acyclic (e.g., linear or branched) Sugar, The glass can be a siliconoxide-containing material in a solid, and the like), and the like. The modified Sugar is a chemically amorphous state without crystallization. Such glass has a high modified furanosyl Sugar or a non-furanosyl Sugar, a furano degree of microstructural disorder due to a lack of long-range Syl Sugar analog, a derivative including a bicyclic Sugar, a order. The glass can include an oxide, for example, silicon morpholino, tetrahydropyran, a cyclohexenyl, a cyclohexitol, dioxide (Sift), aluminum oxide (AlO), barium oxide (BaO), a 2'-modified Sugar, 3'-modified Sugar a 4'-modified Sugar, a bismuth trioxide (BiO), boron oxide (BO), calcium oxide 5'-modified sugar, a substituted compound of any of the fore (CaO), cesium oxide (CsC), lead oxide (PbO), strontium going modified Sugars, or the like. Further, the modified Sugar oxide (SrO), rare earth oxides (e.g., lanthanum oxide includes a structure that replaces afuranose ring of a naturally (La-Os), neodymium oxide (Nd2O), Samarium oxide occurring nucleoside. In certain embodiments, the modified (Sm-O.), cerium oxide (CeO)), and the like. Sugar is a non-furanose ring (e.g., a six-membered ring), or a 0036 An exemplary glass is Sift (e.g., quartz, cristobalite, group having a plurality of rings (fused, non-fused, or spiro). tridymite, and the like). The glass can include Sift and other 0041. In some embodiments, the Sugar monomer is a Sugar components such as elements, for example, aluminum, anti Such as a ribose, deoxyribose, or dideoxyribose. In an mony, arsenic, barium, beryllium, boron, calcium, cerium, embodiment, the Sugar monomer includes a derivative of cesium, chromium, cobalt, copper, gallium, gold, iron, lan ribose, deoxyribose, or dideoxyribose. Such derivatives thanum, lead, lithium, magnesium, manganese, molybde include, e.g., replacement or deletion of a carbon or oxygen num, neodymium, nickel, niobium, palladium, phosphorus, atom in a ring of the sugar with a different atom (e.g., a platinum, potassium, praseodymium, silver, sodium, tanta heteroatom or carbon), inclusion of a double bond in the ring, lum, thorium, titanium, Vanadium, Zinc, Zirconium, and the inclusion of a functional group attached to an atom in the ring, like. The elements can occur in the glass in the form of oxides, or replacement of the ring structure of a cyclic Sugar with an carbonates, nitrates, phosphates, Sulfates, or halides. Further acyclic structure. It is contemplated that any of the ring car more, the element can be a dopant in the glass. Exemplary bons in the Sugar is Substituted with a functional group (e.g., doped glass includes borosilicate, borophosphosilicate, phos alkoxy), or OH or H is attached to the ring carbon atom. In phosilicate, colored glass, milk glass, lead glass, optical glass, Some embodiments, the hydrogen or hydroxyl group of a ring and the like. carbon is modified or replaced with an oxy group, e.g., a 0037. In an embodiment, the glass can include non-amor functional group containing oxygen, or a protecting group. phous, crystalline domains. Such glass can be, for example, a 0042 Exemplary functional groups include alkenyl, salt or ester of orthosilicic acid or a condensation product alkoxy oraryloxy (e.g., OR, wherein R is H. alkyl, cycloalkyl, thereof, e.g., a silicate. Exemplary silicates are cyclosilicates, aryl, aralkyl, heteroaryl or Sugar), alkyl alkylamino, alkyl inosilicates, mesosilicates, orthosilicates, phyllosilicates, thio-alkyl, alkynyl, amide (e.g., NHC(O)R, wherein R is Sorosilicates, tectosilicates, and the like. These glasses have a alkyl, cycloalkyl, aryl, aralkyl, heteroaryl or Sugar), amino structure based on silicon dioxide or isolated or linked SiO, (e.g., NH, alkylamino, heterocyclyl, arylamino, heteroaryl tetrahedral and include other components such as, for amino, or amino acid), aryl, arylamino, cyano, cycloalkyl, example, aluminum, barium, beryllium, calcium, cerium, halo (e.g., F), heteroarylamino, N. heterocyclyl, mercapto, iron, lithium, magnesium, manganese, oxygen, potassium, thioalkoxy, or thioalkyl, which is optionally substituted. Scandium, Sodium, titanium, yttrium, Zirconium, zinc, 0043. In some embodiments, the sugar monomer of the hydroxyl groups, halides, and the like. carbohydrate polymer is a Sugar or Sugar derivative having a 0038. In an embodiment, substrate 6 includes the ceramic. The ceramic is not particularly limited and can be selected cyclic structure as follows: depending on a particular application of article 2. Examples of the ceramic include an oxide-based ceramic, nitride-based ceramic, carbide-based ceramic, boride-based ceramic, sili cide-based ceramic, or a combination thereof. In an embodi ment, the oxide-based ceramic is silica (SiO2) or titania (TiO). The oxide-based ceramic, nitride-based ceramic, car bide-based ceramic, boride-based ceramic, or silicide-based ceramic can contain a nonmetal (e.g., oxygen, nitrogen, boron, carbon, or silicon, and the like), metal (e.g., aluminum, lead, bismuth, and the like), transition metal (e.g., niobium, wherein * (asterisk) is a point of attachment; tungsten, titanium, Zirconium, hafnium, yttrium, and the 0044) Q and Q are independently O, S, Se, NR, CR, or like), alkali metal (e.g., lithium, potassium, and the like), C—CR; alkaline earth metal (e.g., calcium, magnesium, strontium, 0045 Q is O, S, NR, CR, CRCR, CRO, CROCR, and the like), rare earth (e.g., lanthanum, cerium, and the CRS, CRSCR, CRNR, CRNRCR, alkenylene, alky like), or halogen (e.g., fluorine, chlorine, and the like). lene, alkyleneoxy, alkynylene, amide, amine, aralkylene,

US 2015/001785.6 A1 Jan. 15, 2015

-continued polymer, cardlan, carrageenan, cellulose, chitin, chitohex : *- O anose, chitosan, chondroitin, dermatan, dextran, dextran aldehyde, dextrin, diethylamino ethyl dextran chloride, eth ylhydroxyethylcellulose, ficoll, furcellaran, galactocarolose, gellan gum, glucomannan, glycogen, guar gum, gum arabic, hyaluronic acid, hydroxyethylcellulose, hydroxymethylcel lulose, hydroxypropyl methylcellulose, hydroxypropylcellu and the like. lose, hydroxypropyldextran, hydroxypropylethylcellulose, 0052 According to an embodiment, the sugar monomer hydroxypropylmethylcellulose, keratan, maltodextrin, meth includes an acyclic group. The acyclic group can be repre oxy polyethylene glycol, methoxycellulose, methylcellulose, sented by a structure wherein a bond between atoms in, e.g., pectic acid, pectin, pluran, poly(sialic acid), polyethylene ribose ring (e.g., C1'-C2', C2'-C3', C3'-4", C4'-O4, C1'-O4) glycol, polypropylene glycol, polyvinyl pyrrolidone, polyvi or a ring atom (e.g., C1, C2, C3', C4' or O4) independently nylalcohol, pullulan, pustulan, Sodium carboxymethylcellu is absent. lose, sodium carboxymethyldextran, Sodium dextran Sulfate, 0053 Exemplary sugar monomers having an acyclic starch, Succinylated aminodextran, tamarind seed gum, traga structure include canth gum, Xanthum gum, and the like. 0056. In an embodiment, the polysaccharide is ethyl cel HO lulose, hydroxypropyl ethyl cellulose, cellulose acetate phthalate, cellulose acetate, hydroxypropyl methylcellulose No : phthalate, or a combination thereof. According to an embodi 1 Cl 1N, O R, ment, the polysaccharide is chitosan, alginate, carrageenan, pectin, starch, Xanthan gum, gum agar, or a combination R R thereof. R 0057 Starch is a glucose-containing polysaccharide that includes amylose, amylopectin, or combination thereof. Amylopectin is a linear chain polysaccharide, and amylopec tin is a branched chain polysaccharide. It is contemplated amylopectin may be less Soluble in water than amylose due to branching from the polymer backbone. In an embodiment, the starch includes amylose and amylopectin. Starch with a : s S R, high percentage of amylopectin can thicken a fluid composi tion but may not form a gel. It is contemplated that presence S.X.y. YorkR R R of a greater concentration of amylopectin in a composition forms a more viscous composition. It is further contemplated that presence of a greater concentration of amylose in a com position forms a mechanically stronger gel. 0.058 Pectins occur naturally in plant food products and can be used as a gelling agent, stabilizer, or thickener. Exem plary hemicelluloses and pectins include glucuronoxylans, or the like. Xylans, mannans, glucomannans, galactoglucomannans, ara 0054 According to an embodiment, the polysaccharide is, binoxylans, galacturonans, rhamnogalacturonan, Xyloglu e.g., an arabinan, fructan, fucan, fucoidan, galactan, galactu can, and the like. roman, glucan, inulin, levan, mannan, Xylan, and the like. According to an embodiment, the polysaccharide is a 0059 Gums can be an extract from a plant and include homopolymer or a heteropolymer that contains a repeat unit gum tragacanth and guar gum. As highly branched polysac selected from an aldose, ketose, acid, or amine as follows: charides, gums form viscous compositions, trap water among allose, altrose, arabinose, arginine, asparagine, aspartic acid, branches, and are useful as a thickener or stabilizer Polysac cellobiose, cysteine, deoxyribose, dextrose, erythrose, eryth charides include those from aquatic sources such as seaweed rulose, fructose, galactosamine, galactose, galacturonic acid, Such as agars, alginates, and carrageenans. Seaweed polysac glucosamine, glucaric acid, gluconic acid, glucosamine, glu charides are classified as gums, can from a gel, and are useful cose, glucuronic acid, glutamic acid, glutamine, glycine, as a gelling agent, thickener, or stabilizer in compositions. gulose, guluronic acid, histidine, idose, lactose, lysine, lyX ose, maltose, mannitol, mannose, mannuronic acid, 0060. In an embodiment, the carbohydrate polymer of pri neuraminic acid, psicose, ribose, ribulose, serine, Sorbitol, mary intumescent precursor 8 is the nucleic acid that includes Sorbose, Sucrose, tagatose, talose, threonine, threose, treha the Sugar monomer and a nucleobase monomer. lose, tyrosine, Xylose, Xylulose, and the like. 0061. In some embodiments, the nucleobase monomer is a 0055. In an embodiment, the carbohydrate polymer monovalent heterocyclic base of a naturally occurring includes a polysaccharide Such as an agar, agarose, alginic nucleoside e.g., adenine, cytosine, guanidine, uracil, thymi acid, amino dextran, amylopectin, amylose, carboxydextran, dine. Additionally, the nucleobase monomer is naturally carboxylmethylcellulose, carboxymethyl chitosan, car occurring or modified so that the nucleobase monomer boxymethylcellulose, carboxypolymethylene, carboxyvinyl includes, e.g., an analog of a naturally occurring nucleoside.

US 2015/001785.6 A1 Jan. 15, 2015 enine, 6-(alkyl)guanine, 6-(aza)pyrimidine, 6-(aZo)cytosine, second polymer. The first polymer and second polymer inde 6-(aZo)thymine, 6-(aZo)uracil, 6-(methyl)-7-(aza)indolyl, pendently can be a polymer recited above for substrate 6. 6-(methyl)adenine, 6-(methyl)guanine, 6-hydroxyaminopu Accordingly, the first polymer and second polymer are the rine, 6-methyl-7-azaindolyl, 6-thiopurine, 7-(alkyl)guanine, same in an embodiment. In some embodiments, the first poly 7-(aminoalkylhydroxy)-1-(aza)-2-(thio)-3-(aza)-phenox mer and the second polymer are different. azin-1-yl, 7-(aminoalkyl hydroxy)-1-(aza)-2-(thio)-3-(aza)- phenthiazin-1-yl, 7-(aza)indolyl, 7-(deaza)adenine, 0072. In some embodiments, the polymer of secondary 7-(deaza)guanine, 7-(guanidiniumalkylhydroxy)-1-(aza)-2- intumescent precursor 20 has a chemical polarity or a plural (thio)-3-(aza)-phenoxazin-1-yl, 7-(guanidiniumalkylhy ity of charged groups suitable for bonding or interacting droxy)-1-(aza)-2-(thio)-3-(aza)-phenthiazin-1-yl, 7-(guani through attractive electrostatic interactions with substrate 6 or diniumalkylhydroxy)-1,3-(diaza)-2-(oxo)-phenoxazin-1-yl, other components in the intumescent coating 4 such as pri 7-(methyl)guanine, 7-(propynyl)isocarboStyrilyl, 7-azain mary intumescent precursor 8, another secondary intumes dolyl, 7-deaza-inosinyl, 7-methylguanine, 7-propynyl isocar cent precursor 20, and the like. The polymer is neutral in bostyrilyl, 8-(alkenyl)adenine, 8-(alkenyl)guanine, 8-(alkyl) charge or has a net positive or negative charge. adenine, 8-(alkyl)guanine, 8-(alkynyl)adenine, 8-(alkynyl) 0073. Examples of such a polymer area polycation, polya guanine, 8-(amino)adenine, 8-(amino)guanine, 8-(halo) nion, or polar polymer. In one embodiment, the polymer can adenine, 8-(halo)guanine, 8-(hydroxyl)adenine, be cross-linked to provide stretchability to intumescent coat 8-(hydroxyl)guanine, 8-(thioalkyl)adenine, 8-(thioalkyl) ing 4 in order to accommodate a surface strain experienced by guanine, 8-(thiol)adenine, 8-(thiol)guanine, 8-aminogua a flexible substrate 6 or a thermally expanding article 2. nine, 8-aza-7-deaZaadenine, 8-bromoadenine, 8-bromogua Exemplary polymers can include thermoplastics, thermosets, nine, 8-chloroguanine, 8-methylguanine, 8-thioguanine, and polyelectrolytes (including polyampholytes). Such as, 9-(methyl)-imidizopyridinyl, aminoindolyl, dihydrouracil, without limitation, polycarbonate, poly(acrylic acid), poly hypoxanthine, imidizopyridinyl, inosine, inosinyl, isocar (methacrylic acid), polyoxide, polysulfide, polysulfone, fluo bostyrilyl, isoguanisine, N-(methyl)guanine, N3-(methyl) ropolymers (e.g., polytetrafluoroethylene), polyamide, poly uracil, N4-(acetyl)cytosine, N6-(isopentyl)adenine. N6-(me ester, polyurethane, polyimide, poly(vinyl acetate), poly thyl)adenine, N6-isopentyladenine, N6-methyladenine, (vinyl alcohol), poly(vinyl chloride), poly(vinyl pyridine), nitrobenzimidazolyl. nitroimidazolyl. nitroindazolyl, poly(vinyl pyrrolidone), epoxies, polyethylene imine, nitroindolyl. nitropyrazolyl. nubularine, propynyl-7-(aza)in polypropylene imine, polyethylene polyamine, polypropy dolyl, pseudouracil, pyrrolopyrimidinyl, pyrrolopyrizinyl, lene polyamine, polyvinylamine, polyallylamine, chitosan, queosine, tubercidine, uracil-5-oxyacetic acid, uracil-5-oxy polylysine, protamine Sulfate, poly(methylene-co-guanidine) acetic acid methyl ester, Xanthine, 1.3-(diaza)-2-(oxo)-phe hydrochloride, polyethylenimine-ethoxylated, quaternized noxazin-1-yl, 1.3-(diaza)-2-(OXo)-phenthiazin-1-yl, 1.3.5- polyamide, polydiallyidimethyl ammonium chloride-co (triaza)-2,6-(dioxa)-naphthalene, 2.2-dimethylguanine, 2,4- acrylamidem poly(diallyidimethylammonium chloride), (dithio)pseudouracil, 2,4,5-(trimethyl)phenyl-4-(methyl) poly(vinylbenzyltrimethyl-ammonium), poly(acryloxyeth indolyl. 2.6-(diamino)purine, 2,6-diaminopurine, 4-(dithio) yltrimethyl ammonium chloride), poly(methacryloxy(2-hy uracil, 4,6-(dimethyl)indolyl, 4,6-dimethylindolyl, droxy)propyltrimethyl ammonium chloride), poly(N-meth 7-(aminoalkylhydroxy)-1,3-(diaza)-2-(oxo)-phenoxazin-1- ylvinylpyridine), poly(allylaminehydrochloride), y1, 7-(aminoalkylhydroxy)-1,3-(diaza)-2-(oxo)-phenthiazin copolymers thereof, and combinations thereof. Exemplary 1-yl, 7-(guanidiniumalkyl-hydroxy)-1,3-(diaza)-2-(oxo)- polymers also include elastomers, specifically polar fluo phenthiazin-1-yl, N,N-dimethyladenine, N6.N6-(dimethyl) roelastomers. Exemplary fluoroelastomers are copolymers of adenine, and the like. It is contemplated that any of the above vinylidene fluoride and hexafluoropropylene and terpolymers nucleobase monomers can be modified as an analog or Sub of vinylidene fluoride, hexafluoropropylene and tetrafluoro stituted, e.g., O-alkylated, N-alkylated, or a halogenated. ethylene. The fluoroelastomers can be elastomers that include 0069. According to an embodiment, the nucleic acid vinylidene fluoride units (VF2 or VdE), hexafluoropropylene includes a plurality of nucleotides bonded together. The units (HFP), tetrafluoroethylene units (TFE), chlorotrifluoro nucleotides include the nucleobase monomer bonded to the ethylene (CTFE) units, or perfluoro(alkyl vinyl ether) units Sugar monomer, which is bonded to a phosphate group. (PAVE), such as perfluoro(methyl vinyl ether)(PMVE), per Exemplary nucleic acids include ribonucleotides and deox fluoro(ethyl vinyl ether)(PEVE), or perfluoro(propyl vinyl yribonucleotides Such as adenosine monophosphate (AMP), ether)(PPVE). These elastomers can be homopolymers or cytosine monophosphate (CMP), guanosine monophosphate copolymers. Specifically exemplary polymers are fluoroelas (GMP), uracil monophosphate (UMP), deoxyadenosine tomers containing vinylidene fluoride units, hexafluoropro monophosphate (dAMP), deoxycytosine monophosphate pylene units, or, optionally, tetrafluoroethylene units or fluo (dCMP), deoxyguanosine monophosphate (dGMP), deox roelastomers containing vinylidene fluoride units, ythymine monophosphate (dTMP), and monophosphates of perfluoroalkyl perfluorovinyl ether units, tetrafluoroethylene any combination of the Sugar monomer bonded to the nucleo units, and the like. Exemplary polar fluoroelastomers include base monomer recited above. Additionally, the nucleic acid those commercially available from DuPont or Daikin Indus includes non-canonical nucleoside monophosphates (e.g., tries, Ltd. inosine and Xanthine). 0074. In an embodiment, the polymer has a positive charge 0070 Secondary intumescent precursor 20 includes a at a pH of less than 7, specifically less than or equal to 6, more polymer, a blowing agent, cross-linker, acid source, polypep specifically less than or equal to 5, and still more specifically tide or a combination thereof. less than or equal to 4. In an embodiment, the polymer has a 0071. The polymer can be a polymer recited above for negative charge at a pH of greater than 7, specifically greater substrate 6. In an embodiment, substrate 6 includes a first than or equal to 8, more specifically greater than or equal to 9, polymer, and secondary intumescent precursor 20 includes a and still more specifically greater than or equal to 10. US 2015/001785.6 A1 Jan. 15, 2015

0075 Negatively charged polymers include polycarboxy (0083) R' is NH-, -N (alkyl)-, - N(aryl)-, -O-, lic acids such as poly(meth)acrylic acid, salts thereof, or the —C(R') , —S , Substituted or unsubstituted alkylene, like; a polycarboxylic acid copolymer Such as a poly(meth) substituted or unsubstituted arylene, or absent. acrylic acid-co-methyl (meth)acrylate) copolymer, poly(sty I0084. In an embodiment, the nitrogen-containing blowing rene-co-(meth)acrylic acid), poly(styrene-co-maleic acid), agent is a compound or a salt thereof having a structure as and the like, and combinations comprising at least one of the follows: foregoing polymers. As used herein, "(meth)acrylic' means “acrylic' or “methacrylic', and “(meth)acrylate” means N=C-(R), “acrylate' or “methacrylate’, unless otherwise specified. I0085 wherein, for each occurrence of R, R indepen Also as used herein, "copolymer refers to a polymer formed dently is —H, -NH N(H)(alkyl), N(alkyl). - N(H) by the reaction of two or more different monomers, and (aryl), —N(aryl), —COH, -CN. —OH, substituted or therefore encompasses as well the more specific terms “ter unsubstituted alkyl, or substituted or unsubstituted aryl; and polymer, “tetrapolymer and the like. In an exemplary I0086 m is an integer from 1 to 2, depending on the valence embodiment, the negatively charged polymer is polyacrylic Of R. acid, which is water soluble. I0087. In an embodiment, the nitrogen-containing blowing 0076. In another embodiment, the positively charged agent is a compound or a salt thereof having a structure as polymer is an amine-containing polymer. A polyamine may follows: be used Such as those prepared by the polymerization of Q-(R), aziridene and including polyethyleneamines and polyethyl I0088 wherein Q is a five-, six-, seven-, eight-, nine-, or eneimines having a branched structure derived from aziridene ten-membered aryl or heteroaryl cyclic group that contains N and tris(aminoethyl)amine; a hyperbranched or dendrimeric (nitrogen atoms) in the cycle, e.g., a triazine ring: polyamine such as polyamidoamine (PAMAM) dendrimer; a I0089 for each occurrence of R, R independently is—H, polyaminoacrylate Such as poly(N,N-dimethylaminoethyl —OH, -COH, - NO. —CN, substituted or unsubstituted (meth)acrylate); a copolymer thereof with an alkyl or aralkyl amino, substituted or unsubstituted alkyl, or substituted or (meth)acrylate Such as methyl (meth)acrylate, ethyl (meth) unsubstituted aryl; and acrylate, butyl (meth)acrylate, cyclohexyl(meth)acrylate, 0090 n is an integer 0, 1, 2, 3, 4, or 5. 2-hydroxyethy (meth)acrylate, 2-hydroxypropyl (meth)acry 0091. According to an embodiment, the nitrogen-contain late, (meth)acrylonitrile, and the like. Such as, for example, ing blowing agent include any suitable compound that pro poly(N,N-dimethylaminoethyl-(meth)acrylate)-co-(methyl duces N or ammonia, e.g., amines, ureas, guanidines, guan (meth)acrylate); combinations comprising at least one of the amines, S-triazines, amino acids, and salts thereof including above polymers, and the like. In an embodiment, the posi phosphate, phosphonate, phosphinate, borate, cyanurate and tively charged polymer is polyethyleneimine, which is water Sulfate salts, and the like. Exemplary nitrogen-containing soluble. blowing agents include glycine, melamine phosphate, 0077. The blowing agent can be a compound that produces melamine pyrophosphate, melamine polyphosphate, ammo the nonflammable gas, e.g., nitrogen (N), nitrogen oxides nium phosphate, ammonium pyrophosphate, ammonium (NO, NO, and the like), ammonia, carbon, carbon oxides polyphosphate, ethylenediamine phosphate, melamine cya (CO, CO, and the like), water, and the like. nurate, ammonium cyanurate, melamine borate, ammonium 0078. In an embodiment, the blowing agent is a compound borate, and the like. that contains a nitrogenatom in a chain, cycle, heterocycle, or 0092 Additional exemplary blowing agents that contain combination thereof. The nitrogen-containing blowing agent nitrogen include 1,1-dimethylhydrazine, 2-cyanoguanidine, is a compound of or a salt having a structure as follows: 5-aminotetrazole, acesulfame potassium, acetaldoxime, acetone oxime, allophante, aminoacetonitrile, aminoeth ylpiperazine, ammelide, ammeline, aspartame, aZodicarbon amide, benzisothiazolinone, benzoguanamine, benzoguani 0079 wherein, for each occurrence of R, R indepen dine, bilurea, biuret, calcium cyanamide, carbohydrazide, dently is —H, -NH N(H)(alkyl), N(alkyl). - N(H) chloramine, cyanamide, cyanoethylhydrazine, cyanuric acid, (aryl), —N(aryl), —COH, -CN. —OH, substituted or dalfampiridine, diazolidinyl urea, diethanolamine, diethyltri unsubstituted alkyl, or substituted or unsubstituted aryl; and amine, dimethylacetamide, dimethylamine, ethylamine, eth 0080 m is an integer from 1 to 2, depending on the valence ylenediamine, ethylhydrazine, formamidoxime, guanidine, Of R. guanidine carbonate, hexamethylenetetramine, hydrazine, 0081. In an embodiment, the nitrogen-containing blowing hydroxylamine, hydroxyurea, imidazolidinyl urea, isothiaz agent is a compound or a salt thereof having a structure as ole, isothiazolinone, malonamide, malononitrile, melamine, follows: methylamine, methylene blue, nitromethane, piperazine, Sodium azide, sodium dicyanamide, sodium thiocyanate, Suc cinonitrile, tetraethylenepentamme, tetranitromethane, tetra Zole, thiazole, thioacetamide, thiourea, triethylenetetramine, triethylenetetramine, trimethylamine, trinitromethane, urea, 1,2,3-triazole, 1,2,4-triazole, 1.2-cyclohexanedione dioxime, 1.2-dimethylhydrazine, 1,3,5-triazine, 1,3-diaminoguani dine HCl, 1,3-diaminopropane, 1,3-diaminopropane, and the 0082 wherein, for each occurrence of R, R indepen like. dently is —H. —NH, N(H)(alkyl). —N(alkyl). - N(H) 0093 Exemplary triazines include 2,4,6-trichloro-s-triaz (aryl), —N(aryl), —COH, -CN. —OH, substituted or ine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- unsubstituted alkyl, or substituted or unsubstituted aryl; and dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'- US 2015/001785.6 A1 Jan. 15, 2015

methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p- carboxylic acid can be Saturated or unsaturated, branched or methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p- linear, Substituted (e.g., hydroxyl Substituted or amino Sub styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6- stituted) or unsubstituted. bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6- 0.098 Exemplary carboxylic acids include malic acid, tar styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)- taric acid, propionic acid, butyric acid, ascorbic acid, citric S-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis acid, amino acids, chloroacetic acid, dichloroacetic acid, (trichloromethyl)-s-triazine, 2-4-trichloromethyl trichloroacetic acid, trifluoroacetic acid, phthalic acid (in (piperonyl)-s-triazine, and 2-4-trichloromethyl(4'- cluding ortho-, meta- and para-isomers), and the like. methoxystyryl)-s-triazine. 1,3,5-triazine-2,4,6-triamine, 4.6- 0099 Suitable C-C carboxylic acids for use herein can diamino-1,3,5-triazin-2-ol. 6-amino-1,3,5-triazine-2,4-diol. be straight chain or branched chain alkyl or alkenyl structures 1,3,5-triazine-2,4,6-triol, 6-phenyl-1,3,5-triazine-2,4-di or can have a cyclic lactone structure. According to an amine, and the like. embodiment, the carboxylic acid is polyfunctional with 0094. In an embodiment, secondary intumescent precur inclusion of a plurality of carboxyl functional groups such as sor includes the polypeptide. The polypeptide includes a plu lactic acid, ascorbic acid, glycolic acid, mevalonic acid, mal rality of an amino acids bonded together by peptide bonds. onic acid and Succinic acid. Examples of dicarboxylic acids The amino acid is a naturally occurring amino acid or a include, but are not limited to, Oxalic acid, malonic acid, synthetic C. B.Y., or 8 amino acid. Additionally, the amino acid Succinic acid, fumaric acid, maleic acid, malic acid, tartaric includes, amino acids found in proteins, e.g., alanine, argin acid, aspartic acid, glutaric acid, glutamic acid, glutaconic ine, asparagine, aspartate, cysteine, glutamate, glutamine, acid, adipic acid, muconic acid, Suberic acid, itaconic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, and terephthalic acid. Examples of tricarboxylic acids phenylalanine, proline, serine, threonine, tryptophan, include, but are not limited to, citric acid, isocitric acid, aco tyrosine, Valine, and the like. In an embodiment, the amino nitic acid, propane-1,2,3-tricarboxylic acid, and trimesic acid is in an L-configuration. In some embodiments, the acid. amino acid is a derivative of alanyl, argininyl, asparaginyl, 0100 Aromatic carboxylic acids include benzoic acid, aspartoyl, cysteinyl, glutaminyl, glutamyl, glycinyl, histidi orthoatoluic acid, meta-toluic acid, para-toluic acid, ortho nyl, leucinyl, lysinyl, methioninyl, phenylalaninyl, prolinyl, chlorobenzoic acid, meta-chlorobenzoic acid, para-chlo serinyl, threoninyl, tryptophanyl, tyrosinyl, Valinyl, B-alanyl. robenzoic acid, ortho-bromobenzoic acid, metabromoben B-agininyl, B-asparaginyl, 3-aspartoyl, B-cysteinyl, Zoic acid, para-bromobenzoic acid, ortho-nitrobenzoic acid, B-glutaminyl, B-glutaroyl, B-glycinyl, B-histidinyl, B-isole meta-nitrobenzoic acid, para-nitrobenzoic acid, 3,5-dini ucinyl, B-leucinyl, B-lysinyl, 3-methioninyl, B-phenylalani trobenzoic acid, Salicylic acid, meta-hydroxy-benzoic acid, nyl, B-prolinyl, B-serinyl, B-threoninyl, B-tryptophanyl, B-ty para-hydroxybenzoic acid, anisic acid, gallic acid, Syringic rosinyl, B-Valinyl. It is contemplated that, the term "amino acid, anthranillic acid, meta-aminobenzoic acid, para-ami acid is an independent disclosure of each of the esters of C. nobenzoic acid, and the like. Polybasic aromatic carboxylic B, Y, or 6 forms of alanine, arginine, asparagine, aspartate, acids include phthalic acid, isophthalic acid, terephthalic cysteine, glutamate, glutamine, glycine, histadine, isoleu acid, hemimelitic acid, trimelitic acid, trimesic acid, preh cine, leucine, lysine, methionine, phenylalanine, proline, nitic acid, mellophanic acid, pyromellitic acid, diphenic acid, serine, threonine, tryptophan, tyrosine, Valine in the D and L and the like. In some embodiments, a homolog of the aro configurations. Exemplary polypeptides include those con matic carboxylic acid is used in a composition to form intu taining amine functional groups (e.g., primary amines), acid mescent coating 4 and includes phenyl acetic acid, hydrocin functional groups, or a combination thereof. namic acid, gamma-phenylbutyric acid, delta-phenyl-n- 0095. In an embodiment, secondary intumescent precur Valeric acid, epsilon-phenyl-n-caproic acid, cinnamic acid, sor 20 includes the cross-linker. The cross-linker can be a phenylpropiolic acid, homophthalic acid, ortho-phenylenedi hardener, accelerator, catalyst, curative, initiator, and the like, acetic acid, meta-phenylenediacetic acid, paraphenylenedi or a combination thereof. It is believed that the cross-linker acetic acid, ortho-phenylene-acetic-beta-propionic acid, and reacts with functional groups located within intumescent the like. coating 4 such as hydroxyl groups or epoxy groups in various 0101 The amine cross-linker includes a primary, second ways that may include cross-linking, adding to a polymer ary, or tertiary amine, ammonium salt, and the like. Exem backbone, capping a polymer, and the like. The cross-linker plary amine cross-linkers are 1,2-diaminoethane, 1.3-cyclo includes a carboxylic acid, amine, amide, phenol, thiol, anhy hexanedimethanamine, 2,2'-dimethyl-4.4 methylenebis dride, alcohol, or a combination thereof. These cross-linkers (cyclohexylamine), 2,4,6-tris(dimethylaminomethyl)phenol, can enhance properties Such as heat and chemical resistance 2-methylpentamethylenediamine, 2-piperazin-1-ylethy of the resulting intumescent coating 4 or article 2. The cross lamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, linker can be selected based on an identity of primary intu 3-aminopropyldimethylamine, 4,4'-diamino diphenyl mescent precursor 8 or secondary intumescent precursor 20 methane, 4,4'-methylenebis(cyclohexylamine), benzyldim as well as the desired properties of article 2. ethylamine, bis(dimethylamino)methylphenol, 1,3-ben Zene dimethanamine, N(3-dimethylaminopropyl)-1,3- 0096. Examples of the carboxylic acid cross-linker propylene diamine, octahydro-4,7-methano-1H include organic carboxylic acids, hydroxy-carboxylic acids, indenedimethylamine, tetraethylenepentamine, and dicarboxylic acids, such as formic acid, acetic acid, lactic isophoronediamine, triethylenetetraamine, diethylenetri acid, oxalic acid, and the like. amine, aminoethylpiperazine, 1,2-diaminopropane, 1,3-di 0097. In an embodiment, the carboxylic acid is a C-C, aminopropane, 2,2-dimethylpropylenediamine, 1,4-diami carboxylic acid. In one embodiment, the carboxylic acid is a nobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1.8- dicarboxylic acid or a tricarboxylic acid, preferably a dicar diaminooctane, 1.9-diaminonane, 1,12-diaminododecane, boxylic acid, more preferably a C dicarboxylic acid. The 4-azaheptamethylenediamine, N,N'-bis(3-aminopropyl)bu US 2015/001785.6 A1 Jan. 15, 2015

tane-1,4-diamine, cyclohexanediamine, dicyandiamine, dia dithiol-sym-triazine, O 1,3,5-tris(3-mercaptopropyl) mide diphenylmethane, diamide diphenylsulfonic acid isocyanurate; halogen-substituted derivatives of heterocyclic (amine adduct), 4,4'-methylenedianiline, diethyltoluenedi ring-containing thiols; thiol compounds having at least two amine, m-phenylene diamine, melamine formaldehyde, tet mercapto groups and containing Sulfur atoms in addition to raethylenepentamine, 3-diethylaminopropylamine, 3,3'-imi the mercapto groups such as bis-, tris- or tetra(mercaptoalky nobispropylamine, 2.4-bis(p-aminobenzyl)aniline, lthio)benzene, bis-, tris- or tetra(mercaptoalkylthio)alkane, tetraethylenepentamine, 3-diethylaminopropylamine, 2.2.4- bis(mercaptoalkyl)disulfide, hydroxyalkylsulfidebis(mer trimethylhexamethylenediamine, 2,4,4-trimethylhexameth captopropionate), hydroxyalkylsulfidebis(mercaptoacetate), ylenediamine, 1.2-trimethylhexamethylenediamine, 1,3-di mercaptoethyl ether bis(mercaptopropionate), 1,4-dithian-2, amino cyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 5-diolbis(mercaptoacetate), thiodiglycolic acid bis(mercap 1.2-diamino-4-ethylcyclohexane, 1,4-diamino-3,6-diethyl toalkyl ester), thiodipropionic acid bis(2-mercaptoalkyl cyclohexane, 1-cyclohexyl-3,4-diminocyclohexane, 4,4'-di ester), 4.4-thiobutyric acid bis(2-mercaptoalkyl ester), 3,4- aminodicyclohexylmethane, 4,4'-diaminodicyclohexylpro thiophenedithiol, bismuththiol or 2,5-dimercapto-1,3,4-thia pane, 2.2-bis(4-amino cyclohexyl)propane, 3,3'-dimethyl-4, diazol; and the like. 4'-diaminodicyclohexylmethane, 3-amino-1- cyclohexaneaminopropane, 1,3-bis(aminomethyl) 0105 Exemplary phenol cross-linkers include hydro quinone, catechol, resorcinol, phloroglucinol, pyrogallol, cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,6-dihydroxy naphthalene, 2,7-dihydroxy naphthalene, 2,6- m-xylylendiamine, p-xylylendiamine, and the like. dihydroxy naphthalene, 1,2,4-trihydroxybenzene, 1,3-dihy 0102) Exemplary anhydride cross-linkers include maleic droxy naphthalene, 1,4-dihydroxy naphthalene, 1.5-dihy anhydride, tetrahydrophthalic anhydride, hexahydrophthalic droxy naphthalene, 1,7-dihydroxy naphthalene, 2.3- acid, methyltetrahydrophthalic anhydride, methylhexahy dihydroxy naphthalene, 1,2-dihydroxy naphthalene, drophthalic anhydride, 1.2-cyclohexanedicarboxylic anhy 2-methylresorcinol, 5-methylresorcinol, hexahydroxyben dride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, Zene, 1,8.9-trihydroxyanthracene, 3-methyl-pyrocatecho, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-hydroquinon, 4-methyl-pyrocatecho, 4-benzylresor phthalic anhydride, pyromellitic dianhydride, hexahydro cinol, 1,1'-bis(2-naphthol), 4,4'-bisphenol, bis(4-hydrox phthalic anhydride, dodecenylsuccinic anhydride, dichloro yphenyl)sulfone, and 4-bromoresorcinol, 4,4'-butylidenebis maleic anhydride, chlorendic anhydride, tetrachlorophthalic (6-tert-butyl-3-m-cresol), 4-tert-butylcatechol, 2,2'- anhydride, trimelitic anhydride, hexahydrotrimellitic anhy bisphenol, 4,4'-dihydroxydiphenylmethane, tert dride, methylnadic anhydride, hydro methylnadic anhydride, butylhydroquinone, 1,3-bis(4-hydroxyphenoxy)benzene, dodecenyl Succinic anhydride, hexahydropyromellitic dian 1,4-bis(3-hydroxyphenoxy)benzene, 1,1-bis(4-hydroxylphe hydride, benzophenonetetracarboxylic dianhydride, styrene nyl)cyclohexane, bis(4-hydroxyl-3,5-dimethylphenyl)sul maleic anhydride copolymers, dodecyl Succinic anhydride, fone, 9.9-bis(4-hydroxyphenyl)fluorine), 9.9-bis(4-hy and the like. droxyl-3-methylphenyl)fluorine, 4-tert-butyl calix8arene, 0103 Exemplary isocyanate cross-linkers include toluene 4-tert-butyl calix5arene, 4-tert-butylsulfonyl calix4 arene, diisocyanate, methylene diphenyldiisocyanate, hydrogenated calix8 arene, caliX4 arene, calix6 arene, and 4-tety-butyl toluene diisocyanate, hydrogenated methylene diphenyldi calix6 arene, 2.5-bis(1,1,3,3-tetramethylbutyl)hydro isocyanate, polymethylene polyphenylene polyisocyanates, quinone, 2,6-bis(2-hydroxyl-5-methylphenol)methyl-4- isophorone diisocyanate, and the like. methylphenol, 1,1-bis(3-cyclohexyl-4-hydroxylphenol)cy 0104. Thiol cross-linkers include polythiol or polymer clohexane, 1,1-bis(4-hydroxyl-3-methylphenol) captain compounds. In an embodiment, the thiol cross-linker cyclohexane, hexestrol. 2',4'-dihydroxyacetophenone, is an alkyl polysulfide, thiuram disulfide, or amine polysul anthrarufin, chrysazin, 2,4-dihydroxybenzaldehyde, 2,5-di fide. Some non-limiting examples of the thiol cross-linker are hydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, ethyl 4,4'-dithiomorpholine, dithiodiphosphorodisulfides, dieth 3,4-dihydroxyaminobenzoate, 2,4-dihydroxybenzophenone, yldithiophosphate polysulfide, alkylphenol disulfide, tetram 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 4,4'-dihy ethylthiuram disulfide, 4-morpholinyl-2-benzothiazole dis droxybenzophenone, 4-ethylresorcinol, and phenylhydro ulfide, dipentamethylenethiuram hexasulfide, and quinone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-di caprolactam disulfide. Additional exemplary thiol cross-link hydroxybenzophenone, methyl 2,6- ers include aliphatic thiols such as methanedithiol, pro dihydroxyaminobenzoate, 2,3-dihydroxybenzaldehyde, panedithiol, cyclohexanedithiol, 2-mercaptoethyl-2,3-dimer octafluoro-4,4'-bisphenol, 3',6'-dihydroxybenzoylnor capto-Succinate, 2,3-dimercapto-1-propanol (2- bornene, 2,4'-dihydroxydiphenylmethane, 2',5'-dihydroxy mercaptoacetate), diethylene glycol bis(2-mercaptoacetate), acetophenone, 3',5'-dihydroxyacetophenone, 2,4-dihy 1.2-dimercaptopropyl methyl ether, bis(2-mercaptoethyl) droxyaminobenzoate, 2-hydroxyethyl-4,4'- ether, trimethylolpropane tris(thioglycolate), pentaerythritol dihydroxydiphenyl etherdihydroxydiphenyl ether, 2,2'- tetra(mercaptopropionate), pentaerythritol tetra(thioglyco dihydroxydiphenyl ether, methyl 3,5- late), ethyleneglycol dithioglycolate, trimethylolpropane tris dihydroxyaminobenzoate, 1,4-dihydroxy-2-naphthoate, (beta-thiopropionate), tris-mercaptain derivative of tri-gly 3',4'-dihydroxyacetophenone, 2,4'-dihydroxydiphenyl sul cidyl ether of propoxylated alkane, or dipentaerythritol poly fone, 3,4'-dihydroxybenzyl alcohol, 3,5-dihydroxybenzyl (beta-thiopropionate); halogen-substituted derivatives of alcohol. 2,4'-dihydroxybenzophenone, 2,6'-dimethyl hydro aliphatic thiols; aromatic thiols such as di-, tri- or tetra-mer quinone, 2',4'-dihydroxypropiophenone, 4,4'-dihydrxytet captobenzene, bis-, tris- or tetrakis(mercaptoalkyl)benzene, raphenylmethane, methyl 3,4-dihydroxyphenylacetate, 2.5- dimercaptobiphenyl, toluenedithiol, or naphthalenedithiol: dimethylresorcinol, 2-(3,4-dihydroxyphenyl)ethanol, 4,4'- halogen-substituted derivatives of aromatic thiols; heterocy ethylidene bis-phenol, 3,3'-ethylenedioxydiphenol, clic ring-containing thiols such as amino-4,6-dithiol-sym 4-fluorocatechol, ethylgallate, methylgallate, propyl gallate, triazine, alkoxy-4,6-dithiol-sym-triazine, aryloxy-4,6- isoamyl gallate, hexadecyl gallate, dodecyl gallate, Stearyl US 2015/001785.6 A1 Jan. 15, 2015

gallate, butyl gallate, isobutyl gallate, n-octyl-4-hexylresor 0110 ammonium phosphates such as monoammonium cinol gallate, 4,4'-(2-hydroxybenzilidene)bis(2,3,6-trimeth phosphate (NHHPO), diammonium phosphate (NH) ylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 2,2'- HPO, ammonium polyphosphate (NHPOs), and the like; methylene-bis(6-tert-butyl-4-ethyl phenol), 2,2'-methylene 0111 amine phosphates such as melamine phosphates, bis(6-tert-butyl-4-cresol), methoxyhydroquinone, 4,4'-(. e.g., melamine orthophosphate (CHNHOP). alpha.-methylbenzal)bisphenol, 4,4'-methylene-bis(2,6- dimelamine orthophosphate (2CHNHOP), melamine dimethylphenol), 2,2'-methylene-bis(4-methylphenol), pyrophosphate (2CHNHOP), and the like; 5-methoxyresorcinol, 2,2'-methylene-bis(6-(2-hydroxy-5- 0112 trialkyl phosphates such as triethyl phosphate methylbenzyl)-p-cresol. 4,4'-methylene-bis(2-methylphe (CHOP), trioctyl phosphate (CHOP), dimethyl nol), methyl 2,4-dihydroxyaminobenzoate, 2,2'-methylene methylphosphonate, (CHOP), diethyl ethylphosphonate, bis(6-cyclohexyl-p-cresol), methyl 3,4- (CHOP), and the like: dihydroxyaminobenzoate, and 2.5- 0113 halogenated alkyl phosphates and phosphonates dihydroxyaminobenzoate, 2,2',4,4'- Such as tris(2-chloroethyl) phosphate (CHClOP), tris(1- tetrahydroxybenzophenone, 2,4,4'- chloro-2-propyl) phosphate (CHClOP), tris(1,3- trihydroxybenzophenone, 5-methylpyrogallol, 2',4',6'- dichloro-2 propyl) phosphate (CHClOP), tris3-bromo trihydroxypropiophenone, 2,3,4-trihydroxybenzophenone, 2.2-bis(bromomethyl)propylphosphate (CHBrOP), 2',3',4'-trihydroxyacetophenone, 1,1,1-tris(4-hydroxyphe bis(2-chloroethyl)-2-chloroethyl phosphonate, and the like: nol)ethane, 2.3",4,4-tetrahydroxybenzophenone, 4,4',4'-tri 0114 diphosphates such as 2-chloroethyl diphosphates, hydroxytriphenylmethane, 2,3,4,4-tetrahydroxybenzophe e.g., tetrakis(2-chloroethyl), ethylene oxyethylene diphos none, 2,3,4,4-tetrahydroxydiphenylmethane, 5.5".6,6'- phate (CHClOP), CHClOP (available under tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 2,4,5- trade name Antiblaze 100), 2-chloroethyl 2-bromoethyl trihydroxybenzaldehyde, 6,6,7,7-tetrahydroxy-4,44'4'- 3-bromoneopental phosphate (CHBrC1OP) (available tetramethylspirobicromane, tetrafluoro-hydroquinone, 2,3,4- under trade name Firemaster 836); trihydroxybenzaldehyde, 2.2-bis(4-hydroxyphenyl)propane, I0115 cyclic phosphonates such as CHOP (available 2.2-bis(4-hydroxyphenyl)hexafluoropropane, 2.2-bis(2-hy under trade name Antiblaze 19 or 1045), cyclic neopentyl droxy-5-biphenyl)propane, 2.2-bis(3-cyclohexyl-4-hydrox thiophosphoric anhydride, and the like: yphenyl)propane, 2.2-bis(3-sec-butyl-4-hydroxyphenyl)pro 0116 aryl phosphates such as cresyl diphenyl phosphate, pane, 2.2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2.2- (C.H.O.P) and the like: bis(4-hydroxy-3-isopropylphenyl)propane, 2.2-bis(4- 0117 triaryl phosphates such as triphenyl phosphate hydroxy-3-methylphenyl)propane, and the like. (CHOP), tetraphenyl resorcinol diphosphate 0106. Other cross-linkers include boron trihalide amine (Cash2OsP), tris(2,4-dibromophenyl) phosphate adducts of amines Such as monoethanolamine, diethylamine, (CHBrOP), and the like; dioctylmethylamine, triethylamine, pyridine, benzylamine, 0118 diphosphine oxides (available under trade names benzyldimethylamine, and the like. Additional cross-linkers such as Cyagard RF 1204 American Cyanamid); and the like. include phosphine compounds, such as tributylphosphine, 0119. According to an embodiment, the acid source is a triphenylphosphine, tris(dimethoxyphenyl)phosphine, tris bicyclic organophosphorus compound. Exemplary bicyclic (hydroxypropyl)phosphine and tris(cyanoethyl)phosphine; organophosphorus compounds include pentaerythritol phos phosphonium salts, such as tetraphenylphosphonium tet phite, trimethylolpropane phosphite, trimethylolethane phos raphenylborate, methyltributylphosphonium tetraphenylbo phite, trimethylolbutane phosphite, trimethylol isobutene rate and methyltricyanoethyl phosphonium tetraphenylbo phosphite, trimethylol pentane phosphite, trimethylolhexane rate; and the like. phosphite, trimethylolheptane phosphite, trimethylol octane phosphite, trimethylolnonane phosphite, trimethylolunde 0107. In an embodiment, secondary intumescent precur cane phosphite, trimethylolheptadecane phosphite, pen sor 20 includes the acid source. Without wishing to be bound taerythritol phosphate, pentaerythritol thiophosphate, pen by theory, it is believed that the acid source is a dehydrating taerythritol selenophosphate, trimethylolpropane phosphate, agent such as, e.g., an acid or the Salt of an acid that interacts trimethylolpropane thiophosphate, trimethylol propane sele with primary intumescent precursor 8 in intumescent coating nophosphate, trimethylolethane phosphate, trimethylole 4 when article 2 is Subjected to heating. The acid source thane thiophosphate, trimethylolethane selenophosphate, tri includes a Bronsted-Lowry acid, Lewis acid, or a combina methylolbutane phosphate, trimethylol butane tion thereof. In an embodiment, the acid source is introduced thiophosphate, trimethylolpentane phosphate, trimethylol in a form Such as an ester or salt that decomposes in response pentane thiophosphate, trimethylolpentane selenophosphate, to heating to produce acidic residues. The acid source, trimethylolhexane phosphate, trimethylolhexane thiophos includes borates, sulfates, Sulfites, nitrates, phosphates, phos phate, trimethylolheptane phosphate, trimethylolheptane phonates, melamines, and the like. thiophosphate, trimethyloloctane phosphate, trimethyloloc 0108. In an embodiment, the acid source is an oxy-acid tane thiophosphate, trimethylolnonane phosphate, trimethy that includes phosphoric acid, metaphosphoric acid, ortho lolnonane thiophosphate, trimethylolnonane selenophos phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phate, trimethyloldecane phosphate, trimethyloldecane sulfuric acid, and salts thereof. The acid source can be thiophosphate, trimethylolundecane phosphate, trimethylol present, e.g., as an ammonium, amine, or amide Salt of these undecane thiophosphate, trimethylolheptadecane phosphate, acids. trimethylolheptadecane thiophosphate, trimethylolheptade 0109 Exemplary acid sources further include alkyl diphe cane selenophosphate, and the like. nyl phosphates; trimethyl phosphate (CHOP); triph I0120 In an embodiment, the acid source is pentaerythritol enylphosphine oxide (CHOP); triphenyl phosphate phosphate alcohol, which is sometimes referred to as pen (C18H15OP); taerythritol phosphate. Derivatives of the bicyclic phosphorus US 2015/001785.6 A1 Jan. 15, 2015

compounds are contemplated, e.g., esters, ethers, or carbon inosilicate, nesosilicate, phyllosilicate, Sorosilicate, tectosili ates of pentaerythritol phosphate alcohol. cate, or a combination thereof. 0121 According to an embodiment, intumescent coating I0128 Cyclosilicates are silicates with tetrahedrons that 4 includes layered material 10 and a primary intumescent can link to form rings of three (SiO3), four (SiO2), six precursor 8. Layered material 10 includes the layered double (SiOs)' or nine (SiO2) units. Exemplary cyclosili hydroxide, silicate mineral, or a combination thereof. cates include benitoite, axinite, beryl, cordierite, tourmaline, 0122) Layered double hydroxides include a naturally papagoite, eudialyte, milarite, and the like. occurring or synthetic compound based on the mineral bru I0129. The inosilicate can have a crystalline structure in the cite Mg(OH) and have a crystal structure with a plurality of form of a chain Such as pyroxenes and pyroxenoids (with a positively charged layers with a combination of metal crystalline structure of single chains (SiO)') or amphiboles hydroxides between which are a plurality of anions or water (with a crystalline structure of double chains (SiO, )). molecules. Hydrotalcite is a naturally occurring layered Non-limiting examples of pyroxenes and pyroxenoids double hydroxide wherein carbonate is present as the anion. include diopside, spodumene, Wollastonite, enstatite, hyper Meixnerite is a layered double hydroxide wherein hydroxyl is Sthene, hedenbergite, augite, pectolite, diallage, fassaite, Spo present as the anion. dumene, jeffersonite, aegirine, omphafacite, hiddenite, and 0123. In the layered double hydroxide, brucite-like layers the like. Non-limiting examples of amphiboles are calcium include octahedra alternating with interlayers that contain amphiboles such as tremolite, actinote, and hornblende, iron water and charge-balancing anions, which compensate for magnesium amphiboles such as grunerite and cummingto electrostatic charge deficiencies of crystalline clay sheets of nite; and sodium amphiboles such as glaucophane, arfvedso the layered double hydroxide. Exemplary anions include nite, riebeckite; and the like. NO, OH, C1, Br, I, SO, SiO, CrO, BO, 0.130 Non-limiting examples of nesosilicates are alite, MnO, HGaO, HVO4, CIO, BO, pillaring anions almandine, andalousite, andalusite, andradite, belite, chlori such as polyoxometalate anions (e.g., P.W.O., Co. toid, chondrodite, clinohumite, datolite, dumortierite, fay (HO),(PWO)'', H.W.O. V.O.s and alite, forsterite, grossular, humite, hydrogrossular, kyanite, Mo, O...", and the like), monocarboxylates such as acetate, norbergite, olivine, phenakite, pyrope, sillimanite, Spessar dicarboxylates Such as oxalate, alkyl Sulfonates Such as lauryl tine, staurolite, thaumasite, thorite, titanite, topaz, uvarovite, sulfonate, and the like. Zircon, and the like. 0.124. In an embodiment, the layered double hydroxide is I0131 The phyllosilicate includes sheet silicates having a compound with a formula as follows: substantially parallel sheets of silicate tetrahedra with Si-Os in a 2:5 ratio Such as a clay, mica, serpentine, chlorite, or a az combination thereof. Exemplary phyllosicates include aker wherein M(II) is a divalent metal; M(III) is a trivalent metal; matite, aliettite, allophane, aluminoceladonite, amesite, X is the charge-balancing anion: b has a value from /2 to 10; anandite, annite, antigorite, apophyllite, aspidolite, bailey and m and n have a value Such that a ratio of m to n is from 1 chlore, batavite, beidellite, bementite, bensonite, bentonite, to 6, specifically from 2 to 4, and more specifically 3. Exem berthierine, biotite, bismutoferrite, bityite, boromuscovite, plary layered double hydroxides include MgA1CO(OH). borocookeite, bowlingite, brammalite, brindleyite, bronrob 4H2O, Ni Al-CO(OH)4H2O, NiMgA1CO(OH). ersite, brokenhillite, burckhardtite, caryopilite, cavansite, 4H2O, CoMgAlCO(OH)4H2O, CoAll-CO(OH). celadonite, chamosite, champmanite, chernykhite, chlorite, 4H2O, NiocoCoo7sCuoss Mga Al2CO(OH)6.4H2O, chlorite group, chromceladonite, chromphyllite, chrysocolle, CuMgAlCO(OH)4HO CuAl2CO(OH)4H2O, chrysolite; chrysotile, clay mineral group, clinochlore, clin Cu-ZnAll-CO(OH)4H2O, NiZn, Al2CO(OH)6.4H2O, tonite, cookeite, corrensite, cronstedtite, damouzite, Ni3Mg3AlsCroCO(OH)4H2O, and the like. delessite, dickite, donbassite, doZyite, eastonite, eirikite, eph 0.125 Forming layered double hydroxides has been esite, falcondoite, fedorite, ferripyrophyllite, ferrisurite, fer described, e.g., Cavani et al., Hydrotalcite-Type Anionic roaluminoceladonite, ferroceladonite, ferrokinoshitalite, fer Clays, Catalysis Today 11, 173 (1991) and Besse et al., rosaponite, fireclay, fluorannite, fluorophogopite, fraipontite, Anionic clays, in Synthesis and Microporous Materials franklinfurnaceite, friedelite, fuchsite, ganterite, garnierite, (1992), 108 (Van Nostrand Reinhold, 1992), the entire dis gehlenite, glagolevite, glauconite, gonyerite, greenalite, gru closure of each of which is incorporated herein by reference. mantite, gyrolite, halloysite, hectorite, hendricksite, hisinger 0126 Exemplary layered double hydroxides include natu ite, hydrobiotite, illite, imogolite, intersilite, kalifersite, rally occurring minerals from the hydrotalcite Supergroup kaolinite, karpinskite, kegelite, kellyite, kinoshitalite, Such as barbertonite, brugnatellite, caresite, carrboydite, kulkeite, kurumsakite, lalondeite, ledikite, leifite, lepidolite, charmarite, chlormagaluminite, coalingite, comblainite, lizardite, loughlinite, lunijianlaite, macaulayite, makatite, cualstibite, cyanophyllite, desautelsite, droninoite, fougerite, manandonite, manganoneptunite, margarite, martinite, glaucocerinite, honessite, hydrocalumite, hydrohonessite, masutomilite, magillite, medicinal clay, melilite, mica group, hydrotalcite, hydrowoodwardite, iowaite, jamborite, mica, minehillite, minnesotaite, montdorite, montmorillo karchevskyite, kuZelite, manasseite, meixnerite, motuko nite, muscovite, nacrite, nafersite, nanpingite, natrosilite, realite, mountkeithite, muskoxite, natroglaucocerinite, nikis nelenite, neotocite, nepouite, nikSergievite, nimite, nontron cherite, pyroaurite, quintinite, reevesite, shigaite, sjögrenite, ite, norrishite, odinite, okenite, orlymanite, orthochamosite, stichtite, takovite, wermlandite, woodallite, woodwardite, oxykinoshitalite, palygorskite (attapulgite), paragonite, Zaccagnaite, Zincalstibite, Zincaluminite, Zincowoodwardite, pecoraite, pennantite, petalite, phlogite, phlogopite, and the like. According to an embodiment, the layered double polylithionite, preiswerkite, pyrophyllite, pyroSmalite-(fe), hydroxide is hydrotalcite. pyrosmalite-(min), raite, rectorite, reyerite, roscoelite, Sali 0127. In an embodiment, the layered material is the sili otite, Saponite, sarcolite, Sauconite, Schallerite, Sepiolite, cate mineral. The silicate mineral includes a cyclosilicate, sericite, serpentine, serpentine group, shafranovskite, shi US 2015/001785.6 A1 Jan. 15, 2015

rokshinite, shiroZulite, siderophyllite, Smectite, Sokolovaite, lane chemistry, and the like. Without wishing to be bound by spadaite, Stevensite, Stilpnomelane, Sudoite, Suhailite, Surite, the theory, the silicate mineral can have a functional group swinefordite, tainiolite, talc, telyushenkoite, tetraferriphol Such as hydroxyl, amino, Sulfate, phosphate, nitrate, carbo gopite, tetraferriannite, tobelite, to Sudite, trilithionite, tup nyl, carboxyl, imino, and the like on its Surface to interact perssuatsiaite, tungusite, truscottite, ussingite, Varennesite, with primary intumescent precursor 8, secondary intumes Vermiculite, Volkhonskoite, watatsumiite, willemseite, wone cent precursor 20, the additive, and the like. site, yakhontovite, yofortierite, Zakharovite, Zeophyllite, 0.137 According to an embodiment, the silicate mineral is Zincsilite, Zinnwaldite, and the like. a phyllosilicate. In a particular embodiment, the silicate min 0132. The sorosilicate can be allanite, clinozoisite, dol eral is montmorillonite. laseite, epidote, hemimorphite, ilvaite, lawsonite, prehnite, 0.138. In an embodiment, intumescent coating 4 includes tanzanite, Vesuvianite, Zoisite, and the like. the additive, which includes, e.g., a plurality of nanotubes, 0133. The tectosilicate can be, for example, albite, alkali nanofibers, nanoparticles, glass particles, ceramic particles, a feldspars, analcime, andesine, anorthite, anorthoclase, boron source or a combination thereof. The glass particles can bytownite, cancrinite, celsiane, chabazite, coesite, cristo include a glass recited above for substrate 6. The ceramic balite, feldspar, feldspathoid, hauyne, heulandite, labradorite, particles can include a ceramic recited above for substrate 6. laZurite, leucite, marialite, meionite, microcline, mordenite, 0.139. In an embodiment, the additive is the boron source. natrolite, nepheline, nosean, oligoclase, orthoclase, petalite, The boron source can be boric acid, a salt of boric acid, a salt plagioclase, quartz, sanidine, Scapolite, Scolecite, silica, of a hydrate of boric acid that includes Sodium, potassium, sodalite, stilbite, tridymite, Zeolite, and the like. lithium, and the like. Varying degrees of hydration are con 0134 Exemplary zeolites include naturally occurring Zeo templated. lites such as amicite, analcime, barrerite, bellbergite, biki 0140 Exemplary boron sources include a sodium tetrabo taite, boggsite, brewsterite, chabazite, clinoptilolite, cowles rate decahydrate, Sodium tetraborate pentahydrate, sodium ite, dachiardite, edingtonite, epistilbite, erionite, faujasite, octaborate tetrahydrate, sodium metaborate, sodium perbo ferrierite, garronite, gismondine, gmelinite, gobbinsite, gon rate hydrate, disodium octaborate tetrahydrate, potassium tet nardite, goosecreekite, harmotome, herschelite, heulandite, raborate, Sodium pentaborate, ammonium pentaborate laumontite, levyne, maricopalite, maZZite, merlinoite, meso hydrate, hydrasodium tetraborate, potassium metaborate, lite, montesommaite, mordenite, natrolite, offretite, parana alkali metal borate salt, octaborate tetrahydrate (e.g., trolitem, paulingite, pentasil, perlialite, phillipsite, pollucite, NaBO.4H2O, commercially available from IMC Chemi scolecite, Sodium dachiardite, stellerite, stilbite, tetranatro cal), metal borate compounds such as calcium borate, borate lite, thomsonite, tschernichite, wairakite, wellsite, willhend silicate, aluminum silicate borate hydroxide, silicate borate erSonite, and yugawaralite. In some embodiments, the Zeolite hydroxide fluoride, hydroxide silicateborate, sodium silicate is analcime, chabazite, clinoptilolite, heulandite, natrolite, borate, calcium silicate borate, aluminum borate, boron phillipsite, stilbite, or a combination thereof. A synthetic oxide, magnesium borate, iron borate, copper borate, Zinc Zeolite also can be used as the tectosilicate of the silicate borate, sodium polyborate, and the like. mineral. The synthetic zeolites can be selected from Zeolite 0141 Sparingly soluble boron sources include minerals A, Zeolite B, Zeolite F. Zeolite H, Zeolite L, Zeolite T. Zeolite such as probertite, ulexite, nobleite, gowerite, frolovite, cole W. Zeolite X, Zeolite Y. Zeolite Omega, Zeolite ZSM-5, manite, meyerhofferite, inyoite, priceite, tertschite, ginorite, Zeolite ZSM-4, Zeolite P. Zeolite N. Zeolite D, Zeolite O, pinnoite, paternoite, kurnakovite, inderite, preobazhenskite, Zeolite S, and Zeolite Z. hydroboracite, inderborite, kaliborite (heintzite), vealchite, 0135. In an embodiment, the silicate mineral can include and the like. other elements or components in addition to silicon and oxy 0142. It is contemplated that the boron source has a high gen. The silicate mineral can include an oxide, for example, heat activation temperature Such that a high temperatures is silicon dioxide (Sift), aluminum oxide (AlO), barium oxide required to convert the boron Source into an acidic form. (BaO), bismuth trioxide (BiO), boron oxide (BO), cal 0.143 Article 2 includes intumescent coating 4 that is a cium oxide (CaO), cesium oxide (CsO), lead oxide (PbO), product of disposing, on Substrate 6, a composition that strontium oxide (SrO), rare earth oxides (e.g., lanthanum includes primary intumescent precursor 8 and layered mate oxide (LaO), neodymium oxide (Nd2O), Samarium oxide rial 10 such that layered material 10 is dispersed among first (Sm-O.), cerium oxide (CeO)), and the like. An exemplary intumescent precursor 8 in intumescent coating 4. In an silicate mineral containing SiO, includes quartz, cristobalite, embodiment, the composition is a liquid. Accordingly, the tridymite, and the like. The other elements can be, for primary intumescent precursor 8, layered material 10, sec example, aluminum, antimony, arsenic, barium, beryllium, ondary intumescent precursor 20, or additive can be disposed boron, calcium, cerium, cesium, chromium, cobalt, copper, in a solvent to create the liquid composition. gallium, gold, iron, lanthanum, lead, lithium, magnesium, 0144. In an embodiment, a composition to form intumes manganese, molybdenum, neodymium, nickel, niobium, pal cent coating 4 on Substrate 6 includes the solvent, primary ladium, phosphorus, platinum, potassium, praseodymium, intumescent precursor 8 to contact substrate 6 and to form silver, sodium, tantalum, thorium, titanium, Vanadium, zinc, intumescent coating 4 on Substrate 6, and layered material 10 Zirconium, and the like. The other elements can occur in the disposed in the solvent. Primary intumescent precursor 8 silicate mineral in the form of oxides, carbonates, nitrates, includes the carbohydrate polymer. Layered material 10 will phosphates, sulfates, or halides. Furthermore, the other ele be dispersed among primary intumescent precursor 8 in intu ment can be a dopant in the silicate mineral. mescent coating 4 and includes the silicate mineral, layered 0136. It is contemplated that the silicate mineral is func double hydroxide, or a combination thereof. tionalized to include a polar group to form a functionalized 0145 According to an embodiment, the composition fur silicate mineral. Functionalization can be achieved by a cat ther includes secondary intumescent precursor 20 to combine ion exchange reaction, Substitution, condensation, alkoxysi with primary intumescent precursor 8 to form intumescent US 2015/001785.6 A1 Jan. 15, 2015

coating 4 on Substrate 6. In certain embodiments, the compo ate; N.N-dimethylformamide: N,N-dimethylacetamide: sition includes substrate 6 disposed in the solvent. It is con N-methylpyrrolidone; dimethylsulfoxide: gammabutyrolac templated that substrate 6 is substantially insoluble in the tone; pyridine or a derivative thereof, an N-substituted (e.g., solvent. methyl-, ethyl-, formyl-, or acetyl-derivatized) pyrrole, pyr 0146 According to an embodiment, the composition rolidone, piperidine, morpholine, and the like; and the like. includes a solvent. The solvent can be selected so that the first 0152. In an embodiment, the solvent is an amine, includ intumescent precursor, second intumescent precursor, addi ing a primary amine, secondary amine, or tertiary amine oran tive, or layered material have appreciable solubility, can be amine with a plurality of amino groups. Exemplary amines dispersed in the solvent, or is selected to control the available include hexadecyltrimethylammonium hydroxide, n-tetrabu amount of the first intumescent precursor, second intumes tylammonium hydroxide, tetraethylammonium hydroxide, cent precursor, additive, or layered material in the solvent for tetramethylammonium hydroxide, tetrakis(decyl)ammo forming the intumescent coating. In this regard, the solvent is nium hydroxide, dimethylethanol amine, triethanol amine, a polar solvent (e.g., an aqueous solvent) or a nonpolar Sol N-tert-Butyldiethanol amine. Exemplary alkylamines vent. For a first intumescent precursor, second intumescent include ethyl amine, n-butylamine, t-butyl amine, n-hexy precursor, additive, layered material, or Substrate that is lamine, n-decylamine, diethylamine, di(n-propylamine), hydrophobic, a polar solvent can be included in the compo di(iso-propyl amine), trimethylamine, triethylamine, tri(n- sition so that the hydrophobic species is available to be dis butylamine), tetramethyl ethylenediamine, dimethyl ethyl posed on the Substrate. enediamine, ethylenediamine, bis(hexamethylene)triamine, 0147 The solvent may include polar protic solvents, polar N,N',N'-trimethylbis(hexamethylene)triamine, and the like. aprotic solvents, or a combination comprising at least one of these. The solvent may include an electrolyte in the form of a 0153 Exemplary nonaqueous solvents include an ali salt, or a pH adjustment agent (e.g., by addition of acid or phatic hydrocarbon (hexane, heptane, 2,2,4-trimethylpen base), or a buffering agent. tane, n-octane, cyclohexane), an alcohol (e.g., 2-methoxy 0148 An aqueous solvent is, e.g., water, and organic Sol ethanol, butanol, phenol, and the like), an aldehyde (e.g., vents include an alcohol (e.g., methanol, ethanol, isopro acetaldehyde, n-butyraldehyde, crotonaldehyde, 2-ethyl panol, and the like), dimethylsulfone, acetone, an acetate, hexyldehyde, isobutylaldehyde, propionaldehyde, and the dimethsulfoxide, dimethylformamide, Y-butyrolactone, tet like), an amine (e.g., triethylamine, trimethanol amine, and rahydrofuran, propylene carbonate, ethylene glycol, an ether, the like), a nitrogen-containing polar solvent (e.g., N,N-dim an aromatic solvent (e.g., benzene, toluene, p-Xylene, ethyl ethylformamide, nitromethane, N-methylpyrrolidone, and benzene, and the like), or a combination comprising at least the like), a Sulfur compound (e.g., dimethyl sulfoxide), an one of the foregoing. aromatic hydrocarbon (e.g., benzene, toluene, Xylene, and the 0149 Exemplary solvents thus include water including like), a carbonic acid ester (e.g., tetrachloroethylene carbon buffered or pH adjusted water; alcohols, such as methanol, ate, dichloroethylene carbonate, and the like), a carboxylic ethanol, propanol, isopropanol, butanol, t-butanol, octanol, acid (e.g., acetic acid, propionic acid, and the like), an ester cyclohexanol, ethylene glycol, ethylene glycol methyl ether, (e.g., methyl acetate, ethyl acetate, isopropyl acetate, n-pro ethylene glycol ethyl ether, ethylene glycol butyl ether, pro pyl acetate, isobutyl acetate, n-butyl acetate, isobutyl isobu pylene glycol, propylene glycol methyl ether, propylene gly tyrate, 2-ethylhexyl acetate, ethylene glycol diacetate, and the col ethyl ether, diethylene glycol, triethylene glycol, dipro like), an ether (e.g., dimethyl ether, dioxane, tetrahydrofuran, pylene glycol, tripropylene glycol, cyclohexanol, and the methyl celloSolve, and the like), an ether alcohol (e.g., ethoxy like; polar aprotic solvents such as dimethylsulfoxide, Sul ethanol, methoxyethoxyethanol, and the like), an ether ester folane, ethylene carbonate, propylene carbonate, N,N-dim (e.g., ethyl 3-ethoxypropionate and the like), a glycol ether ethylformamide, N,N-dimethylacetamide, N-methylpyrroli ester (e.g., propylene glycol monomethyl ether acetate, eth done, gamma butyrolactone, and the like; or a combination ylene glycol monoethyl ether acetate, ethylene glycol comprising at least one of the foregoing solvents. monobutyl ether acetate, diethylene glycol monobutyl ether 0150. In an embodiment, the solvent is an alcohol, includ acetate, and the like), a halogenated hydrocarbon (e.g., meth ing a primary alcohol, a secondary alcohol, or a tertiary alco ylene chloride, chloroform, carbon tetrachloride, chloroben hol. Exemplary alcohols include methanol, ethanol, (n- or Zene, 1,1,1-trichloroethane, benzoyl fluoride, benzoyl chlo iso-) propanol, (n-, sec-, i-, or t-)butanol, pentanol, octanol, ride, and the like), a ketone (e.g., acetone, cyclohexanone, cyclohexanol, benzyl alcohol, furfuryl alcohol, and the like. acetophenone, 4-hydroxy-4-methyl-2-pentanone, methyl According to an embodiment, the solvent is ethylene glycol ethyl ketone, methyl isobutyl ketone, methyl isoamylketone, or a homolog thereof (e.g., diethylene glycol, triethylene methyl n-amyl ketone, diisobutyl ketone, cyclohexanone, glycol, and the like), propylene glycol or a homolog thereof isophorone, and the like), a phthalate (e.g., dibutyl phthalate, (e.g., dipropylene glycol, tripropylene glycol, and the like), diethyl phthalate, dimethyl phthalate, dioctyl phthalate, dio glycerol or an ether thereof, an ethylene or propylene glycol ctyl terephthalate, butyl octyl phthalate, butylbenzyl phtha monoether (e.g., ethylene glycol methyl ether, ethylene gly late, alkylbenzyl phthalate, and the like), an oil (e.g., mineral col ethyl ether, ethylene glycol butyl ether, propylene glycol oil, silicone oil, and the like), and the like. methyl ether, propylene glycol ethyl ether, and the like), and 0154 Further exemplary nonaqueous solvents include the like. In some embodiments, the solvent is a combination nitromethane, nitrobenzene, acetic anhydride, phosphorus of a celloSolve or a carbitol with another polar solvent, e.g., oxychloride, benzonitrile, tetramethylsulfone, dioxane, 1.2- N-methylpyrrolidone, dimethylformamide, dimethylaceta propanediol carbonate, benzyl cyanide, ethylene Sulfite, mide, dimethylsulfoxide, pyridine, ethylene or propylene isobutyronitrile, propionitrile, dimethyl carbonate, propylene glycol or their higher homologs, glycerol, and the like. carbonate, ethyl methyl carbonate, ethylene carbonate, phe 0151 Exemplary polar aprotic solvents include dimethyl nyl phosphoric acid difluoride, n-butyronitrile, phenyl phos Sulfoxide, Sulfolane; ethylene carbonate; propylene carbon phoric acid dichloride, diphenyl phosphoric acid chloride, US 2015/001785.6 A1 Jan. 15, 2015

trimethyl phosphate, tributyl phosphate, hexamethylphos 0160 Article 2 can be formed in numerous ways. Accord phoric amide, diglyme, polybenzimidazole, and the like. ing to an embodiment, a process for forming article 2 includes O155 These solvents can be used alone or combination. forming a liquid composition by disposing, in a solvent, pri Further, the solvent can be substituted with a functional group mary intumescent precursor 8 that includes a carbohydrate (e.g., an alkyl group, alkenyl group, alkynyl group, or a func polymer and also disposing, in the solvent, layered material tional as recited below for the nanoparticles). 10 that includes a silicate mineral, a layered double hydrox 0156. In some embodiments the solvents is an aqueous ide, or a combination thereof. The process also includes con Solvent. In other embodiments, the solvent is a nonaqueous tacting Substrate 6 with the liquid composition and forming solvent. In yet other embodiments, the solvent includes a intumescent coating 4 on Substrate 6 to form article 2. plurality of water miscible compounds and optionally water 0.161 The process further includes adjusting a pH of the Such that the solvent includes water in an amount less than or Solvent, a temperature of the solvent, or a combination equal to 100 wt %, specifically less than or equal to 80 wt %, thereof. In some embodiments, adjusting the pH of the sol more specifically less than or equal to 50 wt %, further spe vent includes adding an acid, base, or buffer to the solvent. cifically less than or equal to 25 wt %, yet more specifically According to an embodiment, the process also includes treat less than or equal to 10 wt %, or further more specifically less ing substrate 6 with an acid solution (e.g., dilute HNO3) prior than or equal to 1 wt %, based on a total weight of the solvent. to contacting Substrate 6 with primary intumescent precursor In Some embodiments, the solvent contains no water, or water 8 and layered material 10. is substantially absent from the solvent. 0162. Substrate 6 may be untreated or may be surface 0157. In an embodiment, the composition also includes a treated prior to disposing intumescent coating 4 on Substrate pH control agent disposed in the solvent. Exemplary pH 6, e.g., before contacting Substrate 6 with the composition. control agents include an acid (e.g., a mineral acid, organic Surface-treating of substrate 6 may be effected by corona acid, and the like), base (e.g., strong base or weak base), treatment, plasma treatment, chemical vapor treatment, wet buffer, and the like. etch, ashing, primer treatment including polymer based 0158. In an embodiment, first intumescent precursor 8 is primer treatment or organosilane treatment, and the like. In an present in intumescent coating 4 in an amount from 1 weight embodiment, a surface of substrate 6 is treated by corona percent (wt %) to 90 wt %, specifically from 1 wt % to 70 wt treatment prior to contacting Substrate 6 with the composi %, more specifically from 1 wt % to 50 wt %, based on a tion. In another embodiment, the surface of substrate 6 is weight of intumescent coating 4 when dry, e.g., in an absence pre-treated by applying a polymer-based primer layer prior to of solvent. In an embodiment, layered material 10 is present contacting substrate 6 with the composition. An exemplary in intumescent coating 4 in an amount from 2 weight percent primer includes those manufactured by Lord Adhesives and (wt %) to 99 wt %, specifically from 20 wt % to 90 wt %, more marketed under the trade name CHEMLOK. In another specifically from 30 wt % to 80 wt %, based on a weight of embodiment, the surface of substrate 6 may be pretreated by intumescent coating 4 when dry, e.g., in an absence of solvent. dipping Substrate 6 in an organosilane primerto form a primer In an embodiment, second intumescent precursor 20 is layer prior to contacting Substrate 6 with the composition. present in intumescent coating 4 in an amount from 0 weight Such pretreatments serve to enhance the adhesion and bond percent (wt %) to 90 wt %, specifically from 1 wt % to 80 wt ing between Substrate 6 and intumescent coating 4. %, more specifically from 1 wt % to 70 wt %, based on a 0163. In an embodiment, contacting substrate 6 with the weight of intumescent coating 4 when dry, e.g., in an absence composition includes Submerging Substrate 6 in the compo of solvent. In an embodiment, the additive is present in intu sition. Contacting Substrate 6 with the composition includes mescent coating for in an amount from 0 weight percent (wt immersing Substrate 6, Submersing Substrate 6, film casting, %) to 60 wt %, specifically from 0.05 wt % to 40 wt %, more spin casting, dip coating, spray coating, brush coating, roll specifically from 0.5 wt % to 30 wt %, based on a weight of coating, and the like. Such methods can form intumescent intumescent coating 4 when dry, e.g., in an absence of solvent. coating 4 disposed on Substrate 6. 0159. In the composition, a total amount of primary intu 0164. It will further be appreciated that the components of mescent precursor 8 can be from 1 wt % to 90 wt %, specifi intumescent coating 4 can undergo chemical interaction or cally 1 wt % to 70 wt %, and more specifically 1 wt % to 50 transformation to form another material, particularly during wt %, based on a weight of the composition. Secondary heating article 2. As such, embodiments include components intumescent precursor 20 can be present in the composition in of article 2 whether or not a chemical interaction or transfor an amount from 1 wt % to 90 wt %, specifically 1 wt % to 80 mation occurs. That is, embodiments include compositions wt %, and more specifically 1 wt % to 70 wt %, based on the and article 2 of the recited compositions as well as reaction weight of the composition. The additive can be present in the products thereof. composition in an amount from 0.05 wt % to 60 wt %, spe 0.165 Intumescent coating 4, article 2, and methods cifically 0.5 wt % to 40 wt %, and more specifically 0.5 wt % described have beneficial and advantageous properties Such to 30 wt %, based on the weight of the composition. The as imparting fire retardancy to Substrate 6, improving chemi layered material can be present in the composition in an cal or physical change resiliency to Substrate 6, increasing amount from 2 wt % to 99 wt %, specifically 20 wt % to 90 wt explosive decompression resistance, strength, toughness, %, and more specifically 30 wt % to 80 wt %, based on the wear resistance, thermal resistance, heat/electrical conductiv weight of the composition. In a particular embodiment, a ity, and the like to Substrate 6 found in a wide variety, e.g., of weight ratio of primary intumescent precursor 8 to secondary consumer goods. Intumescent coating 4, while serving as a intumescent precursor 20 is from 1:1 to 100:1, specifically 1:1 fire barrier on substrate 6, allows for substrate 6 and articles 2 to 50:1, and more specifically 1:1 to 10:1. In some embodi made therefrom to maintain the physical properties of Sub ment, intumescent coating includes primary intumescent pre strate 6 such as fluid permeability, flexibility, hardness, ten cursor 8 and none or Substantially no secondary intumescent sile strength, glass transition temperature, and the like. precursor 20. Advantageously, disposing primary intumescent precursor 8. US 2015/001785.6 A1 Jan. 15, 2015

layered material 10, and optionally secondary intumescent ible flames in less than 40 sec, more specifically self-extin precursor 20 on Substrate 6 to form intumescent coating 4 guishing of flames in less than 20 sec, and even more specifi occurs in a single step of contacting Substrate 6 with the fluid cally no ignition of article 2. composition. Accordingly, the process of forming intumes 0170 Article 2 and substrate 6 have a substantially similar cent coating 4 on Substrate 6 is fast, reliable, and time effi flexibility, fluid permeability, or a combination thereof. A cient. It is contemplated that the coating process can be thickness of intumescent coating 4 can be from 1 nm to 1 m, repeated a plurality of times to form a plurality of substan specifically from 1 nm to 5 cm, and more specifically from 10 tially identical or different intumescent coatings 4 on Sub nm to 100 nm. strate 6. Moreover, the coating technique used to dispose 0171 Intumescent coating 4 and articles 2 made therewith intumescent coating 4 on Substrate 6 can impart varying have advantageous properties. Intumescent coating 4 is a high thickness intumescent coating 4, based on the desired appli temperature coating with an advantageous decomposition or cation of Substrate 6. Even further, intumescent coating 4 can flame retardant property. In an embodiment, intumescent be applied as a film so thin that a size tolerance of article 4 coating 4 has a thermal decomposition temperature greater based on a size dimension of substrate 6 is not affected by a than or equal to 150° C., specifically greater than or equal to presence of intumescent coating 6, while being thick enough 300° C., and more specifically greater than or equal to 500° C. to impart properties described above on the substrate 6. In a certain embodiment, intumescent coating 4 forms an intumescent product from primary intumescent precursor 8 0166 In an embodiment, intumescent coating 4 and pro and optionally secondary intumescent precursor 20 at a tem cess of forming intumescent coating 4 beneficially comports perature greater than or equal to 50° C., specifically greater with accepted principles of green chemistry as published by than or equal to 150°C., more specifically greater than equal Anastas and Warner, Green Chemistry. Theory and Practice to 300° C., and further more specifically greater than or equal (Oxford University Press: New York, 1998), the disclosure of to SOO C. which is incorporated herein in its entirety. Intumescent coat 0172. The intumescent product formed from primary intu ing 4 and process of forming intumescent coating 4 reduce or mescent precursor 8 and optionally secondary intumescent eliminate a use or generation of hazardous Substances and is precursor 20 has a char content greater than or equal to 35 wt applicable across a life cycle of article 2, including its design, %, specifically greater than or equal to 25 wt %, and more manufacture, and use. specifically greater than or equal to 10 wt %, based on an 0167 Additionally, intumescent coating 4 includes a car original weight (before formation of the intumescent product) bon source, a blowing agent, an acid source, or combination of intumescent coating 4. thereof that comports with green chemistry principles. In an (0173 Various terms are used herein. As used herein, “alk embodiment, primary intumescent precursor 8 and secondary enyl' means a linear or branched chain, monovalent hydro intumescent precursor 20 are independently a carbon Source, carbon group having at least one carbon-carbon double bond a blowing agent, an acid source, or a combination thereof. (e.g., ethenyl (—HC=CH-)). 0.168. It is contemplated that article 2 has fire retardant 0.174 As used herein, “alkenylene' means a linear or properties and is configured to be subjected to a variety of branched chain, divalent hydrocarbon group having at least conditions (e.g., test conditions or conditions while article 2 is one carbon-carbon double bond (e.g., ethenylene in use) that include an ignition source, e.g., a flame source (—HC=CH-)), optionally substituted with one or more (e.g., a candle), Smoldering source (e.g., a cigarette, specifi substituents where indicated, provided that the valence of the cally NIST Standard Reference Material 1196), hot-wire, alkyl group is not exceeded. hot-current, electrical arc, high heat (e.g., an electrical 0.175. As used herein, “alkoxy' means an alkyl group that heater), and the like. is linked via an oxygen (i.e., —O-alkyl). Non-limiting examples of C1 to C30 alkoxy groups include methoxy 0169 Moreover, article 2 has fire retardant properties that groups, ethoxy groups, propoxy groups, isobutyloxy groups, include a maximum amount of heat released (peak heat sec-butyloxy groups, pentyloxy groups, iso-amyloxy groups, release rate, PHRR) that is less than or equal to 300 kilowatts and hexyloxy groups. per square meter (kW/m), specifically less than or equal to 200 kW/m, more specifically less than or equal to 150 0176). As used herein, “alkoxyalkyl means an alkyl radi kW/m, further specifically less than or equal to 100kW/m, cal Substituted with one or more alkoxy groups. and even more specifically less than or equal to 50 kW/m; a 0177. As used herein, “alkyl means a linear or branched total amount of heat released (total heat released, THR) that is chain, Saturated, monovalent hydrocarbon group (e.g., less or equal to 120 megajoules per square meter (MJ/m), methyl or hexyl), optionally substituted with one or more specifically less than or equal to 80 MJ/m, more specifically substituents where indicated, provided that the valence of the less than or equal to 50 MJ/m, and further specifically less alkyl group is not exceeded. Alkyl groups include, for than or equal to 25 MJ/m; an average amount of heat released example, groups having from 1 to 50 carbonatoms (C1 to C50 (average heat release rate, AHRR) that is less than or equal to alkyl). 60 kW/m, specifically less than or equal to 40 kW/m, and 0.178 As used herein, “C1 to C15 alkylamine group' is a more specifically less than or equal to 20kW/m; a percent group of the formula Q-N(Rw)(RZ), wherein Q is a C1 to C15 age mass loss that is relative to starting mass and that is less alkenylene, and Rw and RZare independently hydrogen, a C1 than 60%, specifically less than 40%, more specifically less to C14 alkyl, a C1 to C14 alkenyl, a C1 to C14 alkynyl, a C3 than 20%, further specifically less than 10%, and even more to C14 cycloalkyl or a C6 to C14 aryl; such that the total specifically less than 5%, based on a starting mass of article 2: number of carbon atoms in Q, Rw, and RZ is from 1 to 15. a resistance to ignition (e.g., without an external heat source) 0179. As used herein, “alkylaryl means an alkyl group is ignition then self-extinguishing of visible flames in less covalently linked to a Substituted or unsubstituted aryl group than 60 seconds (Sec), specifically self-extinguishing of vis that is linked to a compound. US 2015/001785.6 A1 Jan. 15, 2015

0180. As used herein, “alkylene' means a linear or structure is obtained. If the cycloalkenylene radical is substi branched chain, Saturated, divalent aliphatic hydrocarbon tuted, this may be so at any desired carbon atom, once again group, (e.g., methylene (—CH2—) or, propylene (-(CH2) provided that a stable structure is obtained. Examples thereof s )). are cyclopentenylene, cyclohexenylene, cycloheptenylene, 0181. As used herein, “alkylene' means a linear, branched cyclooctenylene, cyclononenylene, cyclodecenylene, nor or cyclic divalentaliphatic hydrocarbon group, and may have bornenylene, 2-methylcyclopentenylene, and 2-methylcy from 1 to about 18 carbonatoms, more specifically 2 to about clooctenylene. 12 carbons. Exemplary alkylene groups include methylene 0.195 As used herein, “cycloalkyl means a monovalent (—CH2—), ethylene (-CHCH ), propylene (-(CH) group having one or more Saturated and/or partially saturated ), cyclohexylene (-CH ), methylenedioxy ( O— rings in which all ring members are carbon (e.g., cyclopropyl. CH-O ), or ethylenedioxy (—O—(CH), O—). cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 0182. As used herein, “alkyne” means a linear or branched and partially Saturated variants of the foregoing, such as chain hydrocarbon having at least one carbon-carbon triple cycloalkenyl groups (e.g., cyclohexenyl) or cycloalkynyl bond. groups. 0183. As used herein, “alkynyl means a linear or 0196. As used herein, “cycloalkenyl' means a monovalent branched chain, monovalent hydrocarbon group having at group having one or more rings and one or more carbon least one carbon-carbon triple bond (e.g., ethynyl). carbon double bond in the ring, wherein all ring members are 0184 As used herein, “alkynylene' means a linear or carbon (e.g., cyclopenty1 and cyclohexyl). branched chain divalentaliphatic hydrocarbon that has one or (0197). As used herein, the prefix "hetero” means that the more unsaturated carbon-carbon bonds, at least one of which compound or group includes an atom that is a heteroatom is a triple bond (e.g., ethynylene). (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is 0185. As used herein, "amide' means a group of the for each independently N, O, S, Si, or P. mula C(O) N(RX)(Ry) or N—C(O)—RX, wherein RX is an 0198 Reference herein is made to various heterocyclic alkyl, an alkenyl, an alkynyl, a cycloalkyl or an aryl group; groups. Within Such groups, the term "hetero” means a group and Ry is hydrogen or any of the groups listed for RX. that comprises at least one ring member that is a heteroatom 0186. As used herein, “aryl refers to a hydrocarbon group (e.g., 1 to 4 heteroatoms, each independently N, O, S, P, or Si). having an aromatic ring, and includes monocyclic and poly In each instance, the total number of ring members may be cyclic hydrocarbons wherein the additional ring(s) of the indicated (e.g., a 3- to 10-membered heterocycloalkyl). If polycyclic hydrocarbon may be aromatic or nonaromatic multiple rings are present, each ring is independently aro (e.g., phenyl or napthyl). matic, Saturated, or partially unsaturated, and multiple rings, 0187. As used herein, “arylalkyl means a substituted or if present, may be fused, pendant, spirocyclic or a combina unsubstituted aryl group covalently linked to an alkyl group tion thereof. Heterocycloalkyl groups comprise at least one that is linked to a compound (e.g., a benzyl is a C7 arylalkyl non-aromatic ring that contains a heteroatom ring member. group). Heteroaryl groups comprise at least one aromatic ring that 0188 As used herein, “arylalkylene' group is an aryl contains a heteroatom ring member. Non-aromatic and/or group linked via an alkylene moiety. The specified number of carbocyclic rings may also be present in a heteroaryl group, carbon atoms (e.g., C7 to C30) means the total number of provided that at least one ring is both aromatic and contains a carbon atoms present in both the aryl and the alkylene moi ring member that is a heteroatom. eties. Representative arylalkyl groups include, for example, 0199 As used herein, a "heteroalkyl group is an alkyl benzyl groups. group that comprises at least one heteroatom covalently 0189 As used herein, “arylene' means a divalent group bonded to one or more carbon atoms of the alkyl group. Each formed by the removal of two hydrogen atoms from one or heteroatom is independently chosen from N, O, S, Si, or P. more rings of an arene, wherein the hydrogen atoms may be 0200. As used herein, "heteroarylalkyl means a het removed from the same or different rings (e.g., phenylene or eroaryl group linked via an alkylene moiety. napthylene). 0201 As used herein, "heteroarylene' means a divalent 0190. As used herein, “aryloxy' means an aryl moiety that radical formed by the removal of two hydrogen atoms from is linked via an oxygen (i.e., —O-aryl). one or more rings of a heteroaryl moiety, wherein the hydro 0191 As used herein, an asterisk (i.e., “*)66: denotes a point gen atoms may be removed from the same or different rings of attachment, e.g., a position linked to the same or different (preferably the same ring), each of which rings may be aro atom or chemical formula. matic or nonaromatic. 0.192 As used herein, "cycloalkylene' means a divalent 0202 As used herein, “independently' indicates that the radical formed by the removal of two hydrogen atoms from variable, which is independently applied, varies indepen one or more rings of a cycloalkyl group (a nonaromatic dently from application to application. Thus, in a compound hydrocarbon that comprises at least one ring). such as R"XYR", wherein R" is “independently carbon or 0193 As used herein, “cycloalkynyl' means an aliphatic nitrogen both R" can be carbon, both R" can be nitrogen, or monocyclic or polycyclic group having at least one carbon one R" can be carbon and the other R" nitrogen. carbon triple bond, wherein all ring members are carbon (e.g., 0203 As used herein, “isolated refers to a composition cyclohexynyl). that includes at least 85% to 90% by weight, specifically 95% 0194 As used herein, “cycloalkenylene' means an ali to 98% by weight, and even more specifically, 99% to 100% phatic 5-15-membered monocyclic or polycyclic, divalent by weight of a particular compound in the composition, the radical having at least one carbon-carbon double bond, which remainder comprising other chemical compounds. comprises one or more rings connected or bridged together. 0204 As used herein, “substituted” means a compound or Unless disclosed otherwise, the cycloalkenylene radical can radical Substituted with at least one (e.g., 1, 2, 3, 4, 5, 6 or be linked at any desired carbon atom provided that a stable more) Substituents independently selected from a halide (e.g., US 2015/001785.6 A1 Jan. 15, 2015

F, Cl, Br, I), a hydroxyl, an alkoxy, a nitro, a cyano, an provided evidence that the coating included MMT (Fe, Si,Al, amino, an azido, an amidino, a hydrazino, a hydrazono, a and Na), SPB (S), and starch (C and O). carbonyl, a carbamyl, a thiol, a C1 to C6 alkoxycarbonyl, an 0209. Thermal testing was conducted using cone calorim ester, a carboxyl, or a salt thereof. Sulfonic acid or a salt etry and Smolder ignition testing test. Cone calorimetry was thereof, phosphoric acid or a salt thereof, a C to Co alkyl, a conducted using a standard testing procedure according to C to Ce alkynyl, a C to Co aryl, a C7 to Carylalkyl, a C ASTM standard E-1354-07 with a dual cone calorimeter to Coxyalkyl, a C to Coheteroalkyl, a C to Coheteroaryl operated at an incident target flux of 35kW/m and an exhaust (i.e., a group that comprises at least one aromatic ring, flow of 24 L/s. A cone size sample (5 cmx5 cmx5 cm) was wherein at least one ring member is other than carbon), a C placed in a pan constructed from heavy gauge aluminum foil. to Co. heteroarylalkyl, a C to Co cycloalkyl, a C to Cs Sides and bottom of the sample were covered by aluminum cycloalkenyl, a C to Cs cycloalkynyl, a Cs to Cls heterocy foil, but the top surface was exposed to the cone heater. The cloalkyl, or a combination including at least one of the fore external flux caused the sample to pyrolyze. Once sufficient going, instead of hydrogen, provided that the Substituted fuel (pyrolysis products) were produced, ignition (caused by atom’s normal valence is not exceeded. a spark igniter) occurred, and the sample combusted and 0205 The articles and processes herein are further illus pyrolyzed further. Heat release rate (HRR) as a function of trated by the following examples, which are non-limiting. time was recorded until combustion ceased. In addition to HRR data curves other parameters were reported and EXAMPLES included time to ignition (TTI), maximum amount (peak) of heat released during the test (PHHR), time after ignition to Example 1 reach the PHRR (t-PHRR), total amount of heat released during the test (THR), and average amount of heat released during the test (AHRR). Foam Substrate with Intumescent Coating 0210 Smolder ignition testing was conducted as 0206. A commercially available foam was provided as a described in NIST Technical Note 1747 (http://nylpubs.nist. Substrate to coated with an intumescent coating. The foam gov/nistpubs/TechnicalNotes/NIST.TN. 1747.pdf). The com was a polyether-based polyurethane with nominal air perme ponents of the test included a blue denim cover fabric, a ability of 80 m/min. The following procedure was used to cigarette (available from the U.S. National Institute of Stan produce a coating that included potato starch (commercially dards and Technology as NIST 1196 cigarette), and either a available from Bob's RedMill), sodium polyborate (InCide(R) comparative foam or coated foam, i.e., an article. Technologies Boron #10, SPB), and sodium montmorillonite 0211 FIG. 6 shows a graph of HRR versus time obtained clay (Southern Clay Products Sodium Cloisite(R), MMT) on a from cone calorimeter testing of the comparative foam and polyurethane comparative foam. The composition to be the starch-SPB-MMT coated polyurethane foam that was deposited on the foam was prepared by making the SPB produced following the procedure described above. In FIG. 6, solution, then adding MMT, and then adding the starch. Sev the dotted black line is the starch-SPB-MMT coated polyure eral composition were made, and some compositions did not thane foam. The starch-SPB-MMT coated polyurethane include each component. In one composition, the composi foam had a PHRR of 113 kW/m at 199 s (indicate with an tion did not include SPB so an MMT solution was made with arrow as B), a THR of 50 MJ/m, and an AHRR of 21 kW/m. Subsequent addition of Starch. All deposition and wash com 0212 FIG. 9 is the mass loss from a cigarette ignition test positions were water-based and were prepared using water using a starch-SPB-MMT coated polyurethane foam. purified from a Nanopure II system (18-2 MS2cm, pH of 5.8, 0213. In FIG.9, the average mass loss using a starch-SPB Sybron/Barnstead). MMT coated polyurethane foam after 30 minis 6.7% relative 0207. This procedure was used to create 100 mL of a 3% to the starting mass of the total tested system (i.e., starch starch, 11.5% SPB, and 2% MMT solution. The solution was SPB-MMT coated polyurethane foam and blue denim cover heated (60° C.) and stirred until the SPB fully dissolved and fabric). the reaction to form SPB was complete (30 min). MMT powder (2 mass of the current total mixture) was added to the Example 2 SPB solution. The SPB-MMT solution was stirred for a couple hours. The starch powder (3 mass % of the current Comparative Foam Substrate total mixture) was added to the SPB-MMT solution. Then, the 0214. The comparative foam is the same foam described in solution was heated (90° C.) and stirred until the solution Example 1. formed a gel. Coating began once the solution cooled to 50° 0215. The thermal testing of the comparative foam was C. The foam was Squeezed and released several times in the conducted as described in Example 1. Solution, then left to Soak. After 2 min of soaking, the excess 0216 FIG. 6 is a HRR curve obtained from Cone calorim material was Squeezed out of the sample and the sample was eter testing of the comparative foam and the starch-SPB dried overnight at 70° C. in an air convection oven. MMT coated polyurethane foam that was produced following 0208 FIG. 3 shows a scanning electron microscope the procedure described above. (SEM) micrograph of starch-SPB-MMT coated polyurethane 0217. In FIG. 6, the solid black line is the comparative foam that was produced following the procedure described polyurethane foam. The comparative polyurethane foam had above. The entire surface of the foam is covered by the coat a PHRR of 580 kW/m at 132 s (shown as A), a THR of 121 ing Such that the foam had no exposed surface. FIG. 4 shows MJ/m, and an AHRR of 63 kW/m. The dotted line is starch a higher magnification SEM image of the coating shown in SPB-MMT coated foam. It caused a decrease of all of these FIG. 3. FIG. 5 shows a graph of intensity versus energy for Come measured values (PHRR of 113 kW/m at 199s (shown data acquired by Subjecting the coated foam to elemental as B), a THR of 50 MJ/m, and an AHRR of 21 kW/m. The analysis using an EDEX spectrometer. Elemental analysis starch-SPB-MMT coating also delayed the time to the maxi US 2015/001785.6 A1 Jan. 15, 2015

mum HRR peak from 132 s (A, comparative foam) to 199s 0223. As used herein, “a combination thereof refers to a (B, starch-SPB-MMT coated foam). combination comprising at least one of the named constitu 0218 FIG. 7 shows a graph of total foam mass loss versus ents, components, compounds, or elements, optionally test duration obtained from a cigarette ignition test using a together with one or more of the same class of constituents, comparative foam. In FIG. 7, the average mass loss using a components, compounds, or elements. comparative foam after 30 min is 43.7% relative to the start 0224 All references are incorporated herein by reference. ing mass of the total tested system (i.e., comparative foam and 0225. The use of the terms “a” and “an and “the and blue denim cover fabric). similar referents in the context of describing the invention (especially in the context of the following claims) are to be Example 3 construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Comparative Foam Substrate with Bilayer Coating “Or’ means “and/or” It should further be noted that the terms 0219 Results of cone reduction for the foam of Example is “first.” “second,” “primary.” “secondary.” and the like herein listed in the second row of Table 1. Table 1 also lists (in row do not denote any order, quantity, or importance, but rather 3 to row 8) recently reported flammability reduction of poly are used to distinguish one element from another. The modi urethane foam that includes a fire resistant coating produced fier “about used in connection with a quantity is inclusive of by multilayer assembled coatings, e.g., layer-by-layer (LBL) the stated value and has the meaning dictated by the context coatings. (e.g., it includes the degree of error associated with measure ment of the particular quantity). The conjunction 'or' is used to link objects of a list or alternatives and is not disjunctive; # of Cone Reduction rather the elements can be used separately or can be combined together under appropriate circumstances. Recipes Layers PHRR AHRR THR What is claimed is: 3.0% starch-11.5% SPB-29/o MMT 1 66% 7396 61% 1. An article comprising: O.1% PAA 1.0% LDHSO.1% BPEI 5 41% 79% 32% O.1% PAA.O.1% BPEI 19/o MMT 9 33% 78% 23% a Substrate; and 0.5% (PAA + MMT) pH2/0.5% PEI 10 42% 71.9% 15% an intumescent coating to form an intumescent product in 0.5% CHI/1% (DNA + MMT) 2O 51% 81% 13% response to heating the article, the intumescent coating O.S90 CHI 296 PVS 2O 52% 24% being disposed on the Substrate and comprising: PAACHIPPACHI 2O 55% 20% a primary intumescent precursor comprising a carbohy drate polymer, and 0220. These coatings listed in Table 1 were constructed a layered material comprising a silicate mineral, a lay from synthetic and natural polymers (poly(acrylic acid) ered double hydroxide, or a combination comprising (PAA), branched poly(ethylene imine) (BPEI), chitosan at least one of the foregoing. (CHI), poly(vinyl sulfonic acid) (PVS). DNA), and layered 2. The article of claim 1, wherein the intumescent coating materials (layered double hydroxides (LDH), MMT). The further comprises a secondary intumescent precursor. LbL coatings ranged from 5 monolayers to 20 monolayers 3. The composition of claim 1, further comprising an addi and resulted in a PHRR reduction of 33% to 55%, AHRR tive. reduction of 25% to 81%, and THR reduction of 13% to 32%. 4. The composition of claim 1, wherein the substrate com The one starch-based coatings in Table 1 was produced from prises a polymer, a textile, a metal, a glass, or a combination the procedure described in Example 1. This had a greater comprising at least one of the foregoing. reduction on these properties (66% reduction in PHRR, 73% 5. The composition of claim 4, wherein the substrate is the reduction in AHRR, and 61% reduction in THR). polymer, and the polymer comprises a foam. 0221) While one or more embodiments have been shown and described, modifications and Substitutions may be made 6. The composition of claim 1, wherein the carbohydrate thereto without departing from the spirit and scope of the polymer comprises a polysaccharide, a nucleic acid, or a invention. Accordingly, it is to be understood that the present combination comprising at least one of the foregoing. invention has been described by way of illustrations and not 7. The composition of claim 1, wherein the layered mate limitation. Embodiments herein can be used independently or rial is the layered double hydroxide, which comprises a can be combined. hydrotalcite. 0222 All ranges disclosed herein are inclusive of the end 8. The composition of claim 1, wherein the layered mate points, and the endpoints are independently combinable with rial is the silicate mineral, which comprises a phyllosilicate. each other. The ranges are continuous and thus contain every 9. The composition of claim 2, wherein the secondary value and subset thereof in the range. Unless otherwise stated intumescent precursor comprises a polymer, a polypeptide, a or contextually inapplicable, all percentages, when express blowing agent, a cross-linker, an acid source, or combination ing a quantity, are weight percentages. The Suffix "(s)' as used comprising at least one of the foregoing. herein is intended to include both the singular and the plural 10. The composition of claim3, wherein the additive com of the term that it modifies, thereby including at least one of prises a boron source, a plurality of nanotubes, a plurality of that term (e.g., the colorant(s) includes at least one colorants). nanofibers, a plurality of nanoparticles, a plurality of glass “Optional or “optionally’ means that the subsequently particles, a plurality of ceramic particles, or a combination described event or circumstance can or cannot occur, and that comprising at least one of the foregoing. the description includes instances where the event occurs and 11. The composition of claim3, wherein the first intumes instances where it does not. As used herein, "combination' is cent precursor is present in the intumescent coating in an inclusive of blends, mixtures, alloys, reaction products, and amount from 1% to 90%, based on a weight of the intumes the like. cent coating. US 2015/001785.6 A1 Jan. 15, 2015 20

12. The composition of claim 3, wherein the layered mate primary intumescent precursor being disposed in the rial is present in the intumescent coating in an amount from Solvent and comprising a carbohydrate polymer, and 2% to 99%, based on a weight of the intumescent coating. a layered material to be dispersed among the primary intu 13. The composition of claim 3, wherein the second intu mescent precursor in the intumescent coating on the mescent precursor is present in the intumescent coating in an Substrate, the layered material being disposed in the Solvent and comprising a silicate mineral, a layered amount from 0% to 90%, based on a weight of the intumes double hydroxide, or a combination comprising at least cent coating. one of the foregoing. 14. The article of claim 2, wherein the primary intumescent 19. The composition of claim 18, further comprising: precursor and the secondary intumescent precursor are inde a secondary intumescent precursor to combine with the pendently a carbon Source, a blowing agent, an acid source, or primary intumescent precursor to form the intumescent a combination comprising at least one of the foregoing. coating on the Substrate; and 15. The article of claim 1, wherein the intumescent coating a Substrate disposed in the Solvent, is a product of disposing on the Substrate a liquid composition wherein the substrate is substantially insoluble in the sol comprising the primary intumescent precursor and the lay Vent. ered material, such that the layered material is dispersed 20. A process for forming an article, the process compris among the first intumescent precursor. ing: 16. The article of claim 1, wherein the article has a percent forming a liquid composition by: age heat release rate that is less than or equal to 100. disposing in a solvent a primary intumescent precursor 17. The article of claim 1, wherein the article and the comprising a carbohydrate polymer, and substrate have a substantially similar flexibility, fluid perme disposing in the solvent a layered material comprising a ability, or a combination comprising at least one of the fore silicate mineral, a layered double hydroxide, or a going. combination comprising at least one of the foregoing; 18. A composition comprising: contacting a Substrate with the liquid composition; and a solvent; forming an intumescent coating on the Substrate to form a primary intumescent precursor to contact a Substrate and the article. to form an intumescent coating on the Substrate, the