Ionic liquid flame retardants

Abstract

The present invention relates to the use of ionic liquids as flame retardants. The compounds of the invention may be used as flame retardants in various materials without causing damage to the environment and or health of humans or animals. Ionic liquid flame retardants maybe applied alone or in combination with traditional flame retardants. Ionic liquid flame retardants can be applied to finish textile, plastic, leather, paper, rubber or as wild fire flame retardants.

Claims

1. A flame retardant or flame resistant material, wherein said flame retardant or flame resistant material comprises 80 to 99.9% by weight a base material, and wherein said flame retardant or flame resistant material further comprises 0.01 to about 20% by weight of a flame retardant composition that is homogenously dispersed within said flame retardant or flame resistant material, wherein said flame retardant composition comprises an ionic liquid having the formula: ##STR00023## wherein A is P; and wherein each R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is independently selected from the group consisting of (C.sub.1-C.sub.5)alkyl, and C.sub.6-C.sub.7 aryl; X.sup. is (R.sub.9).sub.2PO.sub.4.sup., and wherein R.sub.9 is selected from the group consisting of (C.sub.1-C.sub.5)alkyl and C.sub.6-C.sub.7 aryl; wherein the base material is acrylate polymer, wherein the presence of said ionic liquid renders said flame retardant or flame resistant material flame retardant or flame resistant compared to the same base material in the absence of said ionic liquid; wherein the flame retardant or flame resistant material has UL94 flammability rating of at least V2.

2. The flame retardant or flame resistant material of claim 1, wherein the ionic liquid having the formula 19: ##STR00024##

3. A method for increasing flame retardant or flame resistant in a base material, said method comprising: providing an ionic liquid in said base material to obtain a flame retardant or flame resistant material comprising from about 0.01 to about 20% by weight of the ionic liquid, wherein the presence of said ionic liquid renders said flame retardant or flame resistant material flame retardant or flame resistance compared to the same base material in the absence of said ionic liquid; wherein the ionic liquid having the formula: ##STR00025## wherein A is N or P; and wherein each R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is independently selected from the group consisting of (C.sub.1-C.sub.5)alkyl and C.sub.6-C.sub.7 aryl; X.sup. is (R.sub.9).sub.2PO.sub.4.sup., R.sub.9SO.sub.3.sup., or R.sub.9SO.sub.4.sup., and wherein R.sub.9 is selected from the group consisting of (C.sub.1-C.sub.5)alkyl and C.sub.6-C.sub.7 aryl; wherein the base material is polymer selected from the group consisting of phenolics, polycarbonates, polyurethanes polyesters, polyethylene, polypropylene, polyacrylate, ethylene-vinyl acetate copolymers, polyamides, epoxy resins, polyvinylchloride resin, and polymethylmethacrylate, wherein the flame retardant or flame resistant material has UL94 flammability rating of at least V2.

4. The method of claim 3 further comprising adding traditional non-halogenated flame retardant to said flame retardant or flame resistant material, wherein said traditional non-halogenated flame retardant is selected from the group consisting of a mineral flame retardant, a phosphorus based flame retardant, a nitrogen based flame retardant, a silicon based flame retardants and nanometric particles, and combinations thereof.

5. The method of claim 3, wherein the ionic liquid having the formula 19 or 20: ##STR00026##

6. The method of claim 3, wherein the ionic liquid having the formula 19: ##STR00027##

7. The method of claim 3, wherein the base material is acrylate polymer.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 provides a list of representative ILs depicted in Formula I, including cyclic and acyclic ILs. In one variation, R and R are each independently selected from the group consisting of (C.sub.1-C.sub.20)alkyl (including CH.sub.3, CH.sub.2CH.sub.3, -allyl, -propargyl, etc . . . ), aryl, (C.sub.3-C.sub.10)heterocyclyl, (C.sub.3-C.sub.10)cycloalkyl, (C.sub.3-C.sub.10)heterocyclyl(C.sub.1-C.sub.8)alkyl, aryl(C.sub.1-C.sub.8)alkyl, heteroaryl and heteroaryl(C.sub.1-C.sub.8)alkyl group that may be unsubstituted or substituted by one or two halo, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxy, NH.sub.2, OH, OR, SH, NHCH.sub.3, N(CH.sub.3).sub.2, cyano, SMe, Si(OR).sub.3, SO.sub.3.sup., SO.sub.3H, CO.sub.2R, P((C.sub.1-C.sub.5)alkyl).sub.2 and P(O)(OEt).sub.2, wherein R is (C.sub.1-C.sub.20)alkyl, (C.sub.3-C.sub.10)cycloalkyl and aryl. In one embodiment of Formula I, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen, (C.sub.1-C.sub.20)alkyl (e.g., CH.sub.3, CH.sub.2CH.sub.3 etc), aryl, (C.sub.3-C.sub.10)heterocyclyl, (C.sub.3-C.sub.10)cycloalkyl, (C.sub.3-C.sub.10)heterocyclyl(C.sub.1-C.sub.8)alkyl, aryl(C.sub.1-C.sub.8)alkyl, heteroaryl and heteroaryl(C.sub.1-C.sub.8)alkyl, unsubstituted or substituted as defined herein; and X.sup.X.sub.1.sup. and are as defined herein.

(2) FIG. 2 illustrates examples of cyclic and acyclic ILs, including an imidazolium IL and a choline based IL. In one embodiment of FIG. 2, X.sup. is as defined herein.

(3) FIG. 3 provides representative examples of heterocyclic ILs, including imidazolium ILs monomers that have functional groups. In one embodiment, n is 1-5; R, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently hydrogen, (C.sub.1-C.sub.20)alkyl, aryl, (C.sub.3-C.sub.10)heterocyclyl, (C.sub.3-C.sub.10)cycloalkyl, (C.sub.3-C.sub.10)heterocyclyl(C.sub.1-C.sub.8)alkyl, aryl(C.sub.1-C.sub.8)alkyl, heteroaryl and heteroaryl(C.sub.1-C.sub.8)alkyl, unsubstituted or substituted; and X.sup. is as defined herein.

(4) FIG. 4 provides a list of representative examples of the anion X.sup. of the ILs. X.sup. anions may also include: [PF.sub.6].sup., [NTf.sub.2].sup., [BR.sub.1R.sub.2R.sub.3R.sub.4].sup., [BF.sub.4].sup., R.sub.2PO.sub.4.sup., RSO.sub.3.sup., RSO.sub.4, OTf.sup., [N(CN).sub.2].sup., [CH.sub.3CO.sub.2].sup., [CF.sub.3CO.sub.2].sup., [NO.sub.3].sup., Br.sup., Cl.sup., I.sup., [Al.sub.2Cl.sub.7].sup., [AlCl.sub.4].sup., [(CF.sub.3SO.sub.2).sub.2N], [(C.sub.2F.sub.5SO.sub.2).sub.2N], [CF.sub.3SO.sub.3], [CF.sub.3BF.sub.3], [(C.sub.2F.sub.5).sub.3PClF.sub.2], [(C.sub.2F.sub.5).sub.3PF.sub.3], [(C.sub.3F.sub.7).sub.3BF.sub.3], [(C.sub.3F.sub.7).sub.3PClF.sub.2], [(C.sub.4F.sub.9).sub.3PClF.sub.2], [(C.sub.4F.sub.9).sub.3SO.sub.3], HS(CH.sub.2).sub.1-3SO.sub.3 and [NiCl.sub.3]; oxalate, dicarboxylates and tricarboxylate, formate, phosphate and aluminate.

(5) FIG. 5 is a depiction of an apparatus for conducting a flammability test.

EXAMPLES

(6) The materials and reagents used are either available from commercial suppliers or are prepared by methods well known to a person of ordinary skill in the art, following procedures described in such references as Fieser and Fieser's Reagents for Organic Synthesis, vols. 1-17, John Wiley and Sons, New York, N.Y., 1991; Rodd's Chemistry of Carbon Compounds, vols. 1-5 and supps., Elsevier Science Publishers, 1989; Organic Reactions, vols. 1-40, John Wiley and Sons, New York, N.Y., 1991; March J.: Advanced Organic Chemistry, 4th ed., John Wiley and Sons, New York, N.Y.; and Larock: Comprehensive Organic Transformations, VCH Publishers, New York, 1989.

(7) In one embodiment, ionic liquids of the present application are further modified by the incorporation with ethereal side chains to provide biodegradable and nontoxic ionic liquids. One such example is shown in FIG. 2. Greener Solvents; Room Temperature Ionic Liquids from Biorenewable Sources, Scott Handy, Chem. Eur. J. 2003, 9, 2938-2944.

(8) ##STR00010##

(9) Hydroxymethyl imidazolium ionic liquid derivatives may be synthesized from fructose according to the method reported by Totter and Handy in Room Temperature Ionic Liquids: Different Classes and Physical Properties; Scott Handy; Current Organic Chemistry, 2005, 9, 959-988; Organic Letter, 2003, Vol. 5, No. 14, pp 2513-2515, Handy et al; Organic Syntheses, Coll. Vol. 3, p. 460 (1955); Vol. 24, p. 64 (1944), Totter et al.

(10) ##STR00011##

(11) The cyclic diaminophosphate compound above may be prepared according to chemistry described by Lall et al in Chem. Comm., 2000, 2413-2414.

(12) ##STR00012##

(13) The allyl imidazolium bromide may be prepared according to chemistry described by Liu et al in Science of China, Series B: Chemistry, 2006, 149, 1, 385-401.

(14) ##STR00013##

(15) The brominated biphenylammonium compound above may be prepared by methylation of the brominated biphenylamine described in Czech patent 233407 titled, Preparation of brominated diphenyl amines as fire proofing agents.

(16) Treatment of Polymers and Resins with IL Flame Retardants:

(17) In one example of polymers containing ILs, the polymer may comprise of about 80 to 99.9 weight percent of the composition that is blended with the IL, and optionally, additive, as provided herein. In one variation, the polymer is a polyolefin. In one variation of the polymer composition, the polyolefin is selected from polypropylene and polyethylene, such as isotactic, atactic and syndiotactic polypropylene, HDPE, LDPE and LLDPE, random and heterophasic copolymers of propylene, ethylene, butene, hexene and octane. In another variation, the polymer is selected from at least one of polyesters, epoxy resins, ABS combinations, halogenated polymers, polyethylene, polystyrene, silicones, silicone rubbers, ethyl vinyl acetate, and their copolymers.

(18) In one aspect of the present application, the polymer is a resin. Such resin may include thermoplastic resin, thermoset resin, thermoplastic resin blend or thermoset resin blend. In one variation, the resin may be selected from polycarbonates, polyamides, polyesters, blends of polycarbonates with other polymers, polyphenylene ether, polyphenyleneoxide, blends of polyphenylene ether with styrenics, blends of polyphenyleneoxide with styrenic materials, polyaramids, polyimides, styrenic materials, polyacrylates, styrene-acrylonitrile resins, halogenated plastics, polyketones, polymethylmethacrylate (PMMA), thermoplastic elastomers, cellulosics, rayon or polylactic acid. In another variation, the polymer employed may be polycarbonates, polycaprolactam, polylauryllactam, polyhexamethyleneadipamide, polyhexamethylenedodecanamide, blends of Nylons with other polymers, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polycarbonate-acrylonitrile-butadiene-styrene blends, polycarbonate-polybutylene terephthalate blends, polyphenylene ether, polyphenyleneoxide, polyphenylene sulfide, polyether sulphone, polyethylene sulfide, acrylonitrile-butadiene-styrene, polystyrene, styrene-acrylonitrile resins, polyvinyl chloride, fluoroplastics, polymethylmethacrylate, thermoplastic urethanes, thermoplastic vulcanizates, or styrene ethylene butylene styrene copolymer.

(19) The resins of may be uncured resins that have no curing agent, semi-cured resins or cured resins. In a particular variation, the amount of the IL that may be incorporated into the resins of the present application may be about 0.01 to about 30% by weight, about 0.01 to about 20% by weight %, about 0.01 to about 10% by weight or about 0.01 to about 5% by weight.

(20) EVA Copolymers:

(21) ##STR00014##

(22) Treatment of ethylene-vinyl acetate (EVA) copolymer with Triethylmethylphosphonium dibutyl phosphate:

(23) EVA (80 g), IL 19 (3 g), low melting glass (5 g) and ATH (alumina trihydrate, 12 g) are mixed, melt blended in a Thermo Haake Rheomix with a screw speed of 60 rpm, and the mixing time is 15 min for each sample. The mixed samples are transferred to a mold and preheated at 180 C. for 5 min and then pressed at 15 MPa, followed by cooling the samples to room temperature while maintaining the pressure for 5 min.

(24) Thermosets with ILs:

(25) ##STR00015##

(26) Phenolic resin (80 g), IL 20 (3 g), glass flake (5 g) and ATH (12 g) are mixed and compounded in a similar manner as described above. The polymers prepared according to the above procedure are found to have flame retardant properties.

(27) Thermoplastics Containing ILs:

(28) ##STR00016##

(29) Polybutylene terephthalate (90 g), IL 21 (7 g), antimony trioxide (3 g) are mixed and extruded in a similar manner as described above. The polymers obtained according to the above procedure are found to have flame retardant properties.

(30) Polycarbonate Polymers with IL:

(31) ##STR00017##

(32) Polycarbonate (90 g), IL 22 (5 g), silicon (3 g) and SnCl.sub.2 (2 g) are mixed and extruded in a similar manner as described above. The polymers obtained according to the above procedure are found to have flame retardant properties.

(33) Incorporation of Functionalized ILs into Polymers:

(34) ILs monomers that have functional groups such as Cl, Br, I, CHCH, CH.sub.2CHCH, -epoxide, OC(O)CHCH, NCO, C(O)Cl, C(O)Br, C(O)-imidazolyl, CO.sub.2(C.sub.1-C.sub.3)alkyl, OC(O)CH.sub.2C(O)CH.sub.3 and CHCR.sub.10CO.sub.2(C.sub.1-C.sub.3)alkyl where R.sub.10 is H or CH.sub.3 may be polymerized into polymers to form polymers containing ILs. For example, ILs containing ethylene oxide groups may be polymerized by initiation with different agents such as postassium t-butoxide in a solvent, such as DMF.

(35) Functionalized ILs Modified Rubber: The modified rubber may be a rubber phase polymer in a matrix containing functionalized ILs. The modified rubber may be prepared by polymerizing the functionalized IL with various rubbers. The modified rubber may be prepared by standard methods such as emulsion polymerization, suspension polymerization, bulk polymerization and by extrusion of a graft copolymer resin and a functionalized IL. The polymerization method employed may provide the modified rubber in about 50% to 90% by weight. In one embodiment, the functionalized ILs may be employed in about 1% to about 30% by weight with the rubber polymer in about 50% to about 95% by weight. Optionally, a copolymerizable polymer may be added in an amount of about 10% to about 30% by weight. Suitable polymers that may be employed include polybutadiene, poly(styrene-butadiene), polyacrylonitrile-butadiene), isoprene rubbers; acrylic rubbers such as polybutyl acrylic acid; and ethylene-propylene rubbers and terpolymers of ethylene-propylene-diene (EPDM). Other copolymers that may be employed in the process include acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide. Other vinyl monomers may be used include -methylstyrene and p-methylstyrene. Additional modified rubber resins may include acrylonitrile-butadiene-styrene (ABS), copolymer resins of acrylonitrile-acrylic rubber-styrene (AAS) and copolymer resins of acrylonitrile-ethylenepropylene rubber-styrene (AES).

(36) In one example, 90 g of butadiene rubber latex powder, 5 g of a selected functionalized IL, 10 g of acrylonitrile and 150 g of deionized water are mixed together. To the mixture is added 0.4 g cumen hydroperoxide and 0.01 ferrous sulfate hydrate. The mixture is heated at about 75 to 85 C. for about 5 hours. The mixture is coagulated to obtain a modified rubber polystyrene resin in a powder form.

(37) In one embodiment, the flame retarding resins may also contain a filler for improving the physical and mechanical properties of the resins. In one aspect, the filler may include glass fibers, glass flakes, glass beads, glass powders, carbon fibers, carbon flakes, talc, mica, kaolin, montmorillonite, bentonite, sepiolite, xonotlite, clay, silica, titanium oxide, carbon black, organic fillers and combinations thereof.

(38) ##STR00018##

(39) A resin containing ILs of the present application may be prepared as follows. A mixture of the epoxide 20a in about 5% to 10% by weight, and an elastomer, about 80 to 95% by weight, containing at least acrylonitrile butadiene rubber containing a carboxyl group, and a hardening accelerator such as an organic phosphine or a phosphonium salt is combined and mixed. Optionally, aluminum hydroxide (0.1% to 5% by weight) and a filler (1% to about 5% by weight) containing talc may be added to the mixture. The mixture may be heated to a temperature of about 180 C. to 270 C. with agitation to form the desired resin. The resulting composition provides a resin that is shown to be flame resistant and the resin has sufficient flexibility and may be used effectively as an electrical insulator. The resin composition prepared according to the method may be used as adhesive insulation that is flame resistant or as printed circuit boards that are flame resistant.

(40) Optionally, other resin additives, including polytrimethylene terephthalate based compounds such as polyethylene terephthalate, polybutylene terephthalate or nylon may be used as a resin additive in the above process to form various fibers and resins containing ILs that are flame resistant.

(41) Incorporation of ILs with Clays:

(42) The clay nanomaterials may be assembled with ILs using macro-scale assembly processes, such as the layer-by-layer (LBL) assembly methods. The method involves the alternating deposition of components from dilute solutions or discpersions on a suitable substrate, including inorganic molecular clusters, nanoparticles, nanotubes and nanowires, nanoplates, dendrimers and clay nanosheets. See for example, P. T. Hammond, Adv. Mater. 16 (2004) 1271. The method allows the formation of multi-functional thin films.

(43) In one example, a mixture of an IL may be combined with a synthetic clay, such as hectorite (Laponite RD) to grow several hundred-nanometers thick films. In certain aspect, the clay may be a montmorillonite or a saponite. Standard layered silicates may also be employed as the clays. The resulting film provides a highly uniform surface coverage of the IL on the substrate, and may form clay multilayers. The nature of the final sheets may depend on various parameters employed, including the adsorption time, the concentration of the IL in the misture, the amount of clay in the dispersion and the pH of the aqueous solution. Thin films of clays and ILs may also be prepared using the traditional dipping method (or dip coating method) or the monolayer deposition method as known in the art. According to the methods, formation of individual nanosheets may be used as flexible fabric, wherein the fabrics are incorporated with flame retardants.

(44) A flame retardant montmorillonite clay may be prepared by modification of a sodium montmorillonite clay with the epoxide 20a by an ion exchange reaction. Optionally, surface functionalization may be performed by grafting with an epoxide group containing a silane compound. The resulting flame retardant clay may be added to an epoxy resin and thermally cured to form various epoxy nanocomposites that are flame retardant.

(45) Similarly, a flame retardant montmorillonite clay may be prepared by modification of a sodium montmorillonite clay with the IL 20b by an ion exchange reaction. The resulting flame retardant clay may be added to an epoxy resin and thermally cured to form various epoxy nanocomposites that are flame retardant.

(46) Molding composition containing ILs may also be prepared. A mixture of a hardener for an epoxy resin, such as phenolic novolak resin, the epoxide 20a (about 5% to 10% by weight) and a quaternary organophosphonium satlt for catalyzing a reaction between the epoxy resin, the hardener and the epoxide 20a. The resulting mixture may be heated to form the flame retardant molding composition that may be used for coating electronic devices.

(47) Flame resistant polyurethanes may be prepared by mixing the epoxide 20a (about 500 g) with diglyme (500 mL) and about 0.5% KOH. The resulting mixture is heated under vacuum, and propylene oxide (495 g) is added. A polyether polyol from bisphenol A, diethanolamine, formaldehyde, propylene oxide and a glycerol-based polyether polyol is added. Mixing and curing the resulting composition at elevated temperatures provide a foam polyurethane having flame resistant properties.

(48) The preparation of nanocomposites comprising ILs may be performed using various methods, including the solvent intercalation route that employs swelling the layered silicates in ILs to promote the diffusion of the ILs in the clay interlayer spacing, or the melt intercalation process which is based on polymer processing in the molten state such as extrusion. See for example, Sinha Ray S, Maiti P, Okamoto M, Yamada K, Ueda K. New polylactide/layered silicate nanocomposites. 1. Preparation, characterization and properties. Macromolecules 2002; 35:3104-10; and Tanoue S, Hasook A, Iemoto Y, Unryu T. Preparation of poly(lactic acid)/poly(ethylene glycol)/organoclay nanocomposites by melt compounding. Polym Compos 2006; 27:256-63, which is incorporate herein in their entirety.

(49) Compounding Treatment of Polyoxymethylene with 1-Butyl-3-methylimidazolium bromide and aluminum hydroxide:

(50) ##STR00019##

(51) Aluminum hydroxide power (5 gm) is premixed with ionic liquid 15 (95 gm), then mixed with polyoxymethylene pellets (900 gm), and then melt-blended by a twin screw extruder at 170-185 C. with a screw rotation speed of 150-180 rpm. The extruded pellets are molded into standard bars for combustibility and mechanical performance tests through an injection-molding machine with a plasticizing temperature of 170-195 C.

(52) Compounding treatment of polypropylene with intumescent flame retarding system using triethylmethylphosphonium dibutyl phosphate 97.0% (CH).

(53) ##STR00020##

(54) A mixture of ionic liquid 16 (2 gm), pentaerythritol (carbonization agent) (5 gm) and melamine (3 gm) are premixed and then mixed with polypropylene (90 gm). The mixture is then melt-blended by a twin screw extruder at 200 C. with a screw rotation speed of 150-180 rpm. The extruded pellets are molded into standard bars for combustibility and mechanical performance tests through an injection-molding machine with a plasticizing temperature of 230 C.

(55) Treatment of PVC Using IL 15 with Antimony Trioxide:

(56) A mixture of IL 15 (5 gm) and antimony trioxide (2 gm) are premixed, and then mixed with polyvinyl chloride resin (93 gm). The mixture is blended and molded into required shape and dimension in a similar manner as disclosed above.

(57) Treatment of PVC Using IL 14 and Traditional Brominated Flame Retardant Tetrabromobisphenol A:

(58) A mixture of IL 14 (3 gm), TBBPA (3 gm) are premixed, and mixed with PVC resin (94 gm). The mixture is blended and molded into required shape and dimension in a similar manner as disclosed above.

(59) Treatment of high density polyethylene (HDPE) with ionic tributylmethylphosphonium methyl carbonate liquid modified clay:

(60) ##STR00021##

(61) The surface of the clay is modified with ionic liquids through ion exchange reaction. HDPE (97 gm) and IL 17 modified clay (3 gm) are mixed, melt blended in ThermoHaake Rheomix with a screw speed of 60 rpm, and the mixing time for each sample is 15 min. The mixed samples are transferred to a mold and preheated at 180 C. for 5 min and then pressed at 15 MPa followed by cooling them to room temperature while maintaining the pressure for 5 min.

(62) Treatment of polyimide 6 with ionic liquid/carbon nanotubes or ionic liquid/carbon nanofibers using 1-butylpyridinium bromide:

(63) ##STR00022##

(64) A mixture of IL 18 (3 gm) and carbon nanotubes or nanofibers (2 gm) are premixed, and then melt-blended and molded in a similar manner as disclosed above. Treatment of polystyrene via in-situ polymerization method:

(65) A mixture of styrene (95 g), IL 15 (5 g), AIBN (0.2 g) is prepared. The mixture is stirred magnetically under nitrogen at room temperature until a homogenous mixture is formed. The mixture is heated at 90 C. for pre-polymerization until a critical viscosity of the mixture is reached. The mixture was then transferred to an oven and kept isothermally at 60 C. for 24 h and then at 80 C. for 20 h. A copolymer containing IL is obtained.

(66) Application IL Flame Retardants as a Components of Coating or Paint Layers:

(67) Ionic liquid flame retardant 16 (5 g) is mixed with 250 ml of paint and coating materials. The resulting material is used as a heat resistant or flame resistant coating on potentially flammable surfaces. Heating of the coated materials shows that the materials are heat resistant or flame resistant to about 455 C. The coating composition may include those formulated form modified epoxy ester resin coating, modified silicone-alkyd resin coating, specially modified silicone acrylic resin and modified silicone acrylic.

(68) The polymers containing the ILs prepared according to the methods above, for example provides significantly improved UL94 test characteristics.

(69) Flame Retarding Finishing of Cotton Textile Materials:

(70) Flammable fabrics may be treated to minimize burning hazards. One such treatment involve fiber copolymerization wherein one or more fiber monomers that are flammable are combined and copolymerized with fire retardant fibers, resulting in improved properties of the fabric. In one aspect, the fire or flame retardant fibers are treated or impregnated with ionic liquids (IL) of the present application. In another aspect, the IL may be introduced onto the fibers or fabrics using chemical post treatment method by coating the fabric or by the introduction of the IL into the fabric by impregnating the fabric with the IL during the dyeing of the fabric. According to these methods, the IL are bound to the fabric and do not readily migrate from the fabric into the environment.

(71) Cationic softening agentssuch as one or more of polyolefins, modified polyolefins, ethoxylated alcohols, ethoxylated ester oils, alkyl glycerides, fatty acid derivatives, fatty imidazolines, paraffins, halogenated waxes, and halogenated estersare used instead to impart softness to the treated fabric. A single softening agent or a combination of different softening agents may be used.

(72) Stain and water repellant agents of the present application may include fluoropolymers, waxes, silicones and polysiloxanes, hydrophobic resins, commercially available fluoropolymers and combinations thereof.

(73) Coating of the ionic liquid flame retarding composition according to the present method allows the coating composition to retain its properties without flaking or melting even after exposure to heat or fire. The coating composition also provides fabrics that are durable for multiple launderings.

(74) In certain embodiments for the use of the flame retardants on fabrics, softeners may be used and may include polydimethylsiloxane, aminosiloxane and quarternary silicone softeners.

(75) A finishing aqueous solution containing 7% by weight IL flame retardant 11 is prepared. The cotton fleece is first immersed in the solution, then passed through a laboratory padder with two dips and two nips, dried at 90 C. for 3 min 45 s, and finally cured in a Mathis oven at 170 C. for 4 min.

(76) Flame Retarding Finishing of Leather Materials:

(77) A finishing aqueous solution containing 7% by weight flame retardant 16 is prepared. The finishing of leather can be done in a similar manner as used in textile finishing.

(78) Flame Retarding Treatment of Wood:

(79) An aqueous impregnation solution is prepared containing 7% by weight IL 16. Test panels are prepared on A angustifolia. The impregnations are carried out at 201 C. in a vertical Pressure vessel of 251 capacity, provided with a vacuum pump and an air compressor. In all the cases, the vessel is loaded with the test panels to be impregnated; then the pressure is reduced by 400 mmHg for 30 min to remove air and vapor from the wood cells. The impregnants are added at the reduced pressure. After about 5 minutes, the pressure is gradually increased until a final pressure of 4780 mmHg (6.5 kgcm.sup.2) to facilitate the penetration; this stage lasts for 120 min. Next, the pressure is reduced to a light vacuum (approximately 50 mmHg for 10 min) to eliminate the excess of solution. Finally, the test panels are removed and rinsed with distilled water.

(80) Flame Treatment of Paper:

(81) An aqueous finishing solution containing 7% by weight IL 16 is prepared. The paper is treated by soaking the samples in the finishing solution for 10 min. The excess solution is removed by pressing the samples between two roll mills of a manually operated wringer.

(82) Wild Fire Protection:

(83) Flame Retardant Preparation

(84) For a representative demonstration, triethylammonium phosphate was employed as a simple analogue of choline phosphate. Triethylammonium phosphate was prepared from reacting triethylamine and phosphoric acid at a 3:1 molar ratio. The retardant solution was used without further characterization.

(85) Sample Preparation

(86) Small ginkgo tree branch samples of approximately equivalent size were taken from University of the Colorado at Boulder campus. All samples were oven dried at 120 C. for 24 hours. Branch samples were soaked in the triethylammonium phosphate flame retardant solution for 5 seconds. Then the samples were taken out of the solution, and hung in still air for 20 minutes to remove excess retardant solution. The samples were then further dried for another 24 hours at room temperature. Controlled sample using pure water treatment were prepared and dried in the same way.

(87) Flammability Test

(88) UL 94V, a simple test of vertical combustion, is employed for flammability testing. The corresponding experimental device is shown in FIG. 5. The burner was controlled to produce a blue flame with a 20 mm high central cone and a power of 50 W. The flame was applied to the bottom of the sample and the top of the burner was located at 10 mm from the bottom edge of the sample. The flame is applied for 10 seconds and removed. The after flame time t1 (the time required for the flame to extinguish) is noted. After extinction, the flame is applied for another 10 seconds. The after flame time t2 is noted, together with the afterglow time t3 (the time required for the fire glow to disappear).

(89) TABLE-US-00001 TABLE 1 After flame times of treated and control samples After Flame Time TEAP Treated Sample Control Sample T1 3 s 6 s T2 3 s 7 s T3 1 s 324 s

(90) As is apparent from these experiments, the after flame time of samples treated with triethylammonium phosphate is significantly shorter than those of the control samples, which clearly show the capacity and efficiency of ammonium phosphate ionic liquids as effective flame retardants.

(91) Flame Retardants for Fighting Forest Fires:

(92) 50 weight % mixture of IL 12 is prepared and sprayed in a controlled forest area containing evergreens such as pines, spruces and fir trees and shrubs for demonstrating the effectiveness of the use of IL for fire protection for wild forest fires. The controlled burn area was ignited, allowed to burn for about 3 minutes, and the IL prepared according to the procedures provided herein were sprayed over the fire. The active fire was extinguished almost immediately and the unburned evergreens were protected from any residual flames. In one variation of the procedure, the IL may be mixed with water and high viscosity gum thickeners to form the IL flame retardant. Optionally, colorant such as an off-white color or red iron oxide may be added.

(93) In another example, the IL may be combined with ammonium polyphosphate, diammonium phosphate, monoammonium phosphate, attapulgus clay, guar gum or a derivative of guar gum, and combinations thereof to form the IL composition for treating forest fires. In another example, the IL of the present application may be mixed or combined with commercial fire or flame retardants such as PHOS-CHEK D75 to provide a highly effective fire retardant composition. Such high viscosity composition provides accurate drop characteristics and highly effective penetration through forest canopy.

(94) While a number of exemplary embodiments, aspects and variations have been provided herein, those of skill in the art will recognize certain modifications, permutations, additions and combinations and certain sub-combinations of the embodiments, aspects and variations. It is intended that the following claims are interpreted to include all such modifications, permutations, additions and combinations and certain sub-combinations of the embodiments, aspects and variations are within their scope.