CA2907221A1 - Functionalized ionic liquids and their applications - Google Patents

Abstract

Disclosure of fmictionalized ionic liquids. 'Use of disclosed ionic liquids as solvent for carbon dioxide. Use of disclosed ionic liquids as flame retardaat. Use of disclosed ionic liquids for coating fabric to obtain flame reiardani fabric.

Description

INVENTORS:
Krishnaswamy Kasthuti Rangan (Fairfax, VA), 1-lumeha Krishnamurthy Hariprakasha (Frederick, MD), Tirumalai Stinivas Sudarshan (Vienna, VA) FUNCTIONALIZED IONIC LIQUIDS AND THEIR APPLICATIONS
RELATED APPLICATIONS
[1.1 This Application claims priority from co-pending US Application Serial No. 61787788, filed on March 15, 2013 which is incorporated in its entirety by reference.
.FIELD

[2] This disclosure relates to synthesis of new ionic liquids containing amine and alcohol groups and their applications.

[3] This disclosure provides details about the synthesis of new type of ionic liquids functionalized with primary, secondary or tertiary amine groups along with hydroxyl groups in the sample molecule.

[4] This disclosure provides details on the application amine and hydroxyl functionalized ionic liquid in carbon dioxide absorption.

[5] This disclosure provides details on the application amine and hydroxyl functionalized ionic liquid in flame resistant. articles.

BACKGROUND

[6] In this section, we discuss several aspects of related work, including background and conventional technologies.

[7] Ionic liquids by definition are salts that have melting points below 100 degree C. Interest in ionic liquids has grown markedly in recent years because of their potential applications in a wide range of fields including, Electroplating, Lubricant, Antistatic coating, Cleaning. Powder coating, Fire resistant treatment, Electrolytes in supercapacitors, fuel cells, lithium ion batteries, and lithium, batteries, separations techniques such as Liquid-liquid extraction, Treatment of nuclear waste, Desulfurization ofDiesel, Metal extraction, Gas purification and Membranes, solvents or reaction medium in Organic reactions, Acid catalysis, Immobilization catalystin Synthesis of nanoparticles, in biotechnology applications such as Biomass conversion, Protein purification. and Enzymatic reactions, Matrices of mass spectroscopy, and Chromatography and solvents for catbon dioxide capture, sulfur dioxide capture and hydrogen. sulfide capture.
[8.1 Ionic liquids are mainly composed. of organic cations, such as alkylammonium, alkylphosphonium, alkylsulfonium, dialkylimidazolium, alkyltriazolium, alkylpyridinium. etc. and mononuclear anions, such as 13Fsub.4. PFsub.6, eFsub3S0sub.3, (CFsub.3S0sub.2)sub.2N, methide, CFsub3COsub.2. Some ionic liquids .containing non-fluomanions, such as nitrate, perehlorate, alkyl sulfate and alkyl oligoether sulfate, dinitramide, amino acid anions. A variety of organic anions, have also been synthesized and studied. The chemical structure of the typical cations and anions comprised by ionic liquids are provided in Figure [9] '1' he chemistry of cation and the anion determines the Physical and chemical properties of an ionic liquid. Therefore, it is:possibletoaChieve.
specific physical property by choosing the proper combination of a cation and an anion. For example, the viscosities can be adjusted over a wide range of less than 50 el' to .greater than 1.0õ000 cP.
[101 Carbon dioxide absorption by ionic liquids [11] There are two types of ionic liquids currently pursued in research field (1) Room temperature ionic liquids (RT1Ls), and (2) Ta*,5pecific or functionalized ionic liquids High-pressure phase behavior of carbon dioxide with a variety of ionic liquids was first reported back in 2.001 by Blanchard et al. Their study included ionic :liquids,-1.-n-butyl:3-methylimidazolium hexafluorophosphate, 1-n-ootyI-3-methylimidazolium hexafluorophosphate, 1-n-oety1-3-methylimidazolium tetrafluoroborate,. 1-n-buty1-3-methylimidazolium nitrate, I -ethyl-3-Methylimidazolium ethyl sulfate, and N-butylpyridinium tetrafluoroborate. The researchers Observed that a large quantity of carbon dioxide could be dissolved in the ionic liqu.id phase.
[12] This research group also latter showed that ionic liquids with the bis(trifluoromethylsulfonyt) imide anion had the largest affinity for carbon dioxide regardless of whether the cation, was imidazolium, pyrrolidinium, or tetraalkylammonium. These results suggest that the nature of the anion has the most significant influence on the carbon dioxide solubility. The solubility of carbon dioxide in a series of imidazolium-based room--temperature ionic liquids has been determined by Baltus et al [13] With the aim of finding ionic liquids that improve carbon dioxide solubility and to understand how to design carbon dioxide-ph ilic ionic liquids, Muldoon et al studied the low- and high-pressure measurements of carbon dioxide solubility in a range of ionic liquids possessing structures likely to increase the solubility of carbon dioxide. They examined the carbon dioxide solubility in a number of ionic liquids with systematic increases in fluorination. They also found that the anion plays a key role in determining carbon dioxide solubility in ionic liquids in agreement with other research reports.
[14] Thus the literature reports indicate that fluoride containing anions bis[trifluoromethyl sultbnyl] amide and Iris (trifluoro methyl sulfonyl) mean& [methidej are most suitable as anions in the new ionic liquids for carbon dioxide capture.
DM The viscosity of common room temperature ionic liquids is quite high.
For example, I-n-buty1-3-methylimidazolium tetrafhtoroborate (79.5 cP) is found to be 40 times more viscous as compared to 30 percent monoethanolamine solution at the same temperature (33 Cp). in order to meet the viscosity constraints, ionic liquids can be mixed with some common organic solvents or water. However, inclusion of such liquids will accompany their own drawbacks as well or this may be accomplished at the expense of decrease in gas capture ability. For example, addition of polyethylene glycol to an ionic liquid decreased the carbon dioxide [16] Without wishing to bind by any theory, based on the above discussion following conclusions can be arrived: (a) Room temperature ionic liquids themselves have shown adequate level of carbon dioxide solubility and (b) Mixing chemically absorbing species such amines, alcohols and amino alcohols with ionic liquids can shift the equilibrium towards higher carbon dioxide absorption even at low carbon dioxide partial pressures [17] Chemical structural .features.crucial for carbon dioxide absorption [18] There are over lOsup.18 ionic liquids available for exploration. It is not practical to synthesize every one of these compounds and select the best ionic liquid for carbon dioxide absorption. Therefore, ionic liquids containing cations in which amino and alcohol functional groups present in the same molecule was judiciously selected. The rationale behind this selection of these functional groups is discussed below.
[19] The state-of-the-art technology for carbon dioxide capture is reversible chemical absorption into an aqueous amine solution. The capacity of an aqueous amine solution to chemically absorb carbon dioxide is a function of the route by which carbon dioxide reacts with the amine. There are two chemical routes generally considered for chemical absorption of carbon dioxide by amines.
[20] Route I (carbamate formation Amine : carbon dioxide 2:1) [21] Amines can react with carbon dioxide to form a carbamic acid (Rsub.2NCOOEI).
[22] CARBON DIOXIDE Rsub.2N14 ---> Rsub.2NC0011 (carbamic acid) [23] Depending upon its acidity, it may then give up a proton to a second amine molecule forming a carbamate (R2NCOOsup.-).
[24] Itsub.2NCOOEI ---> R2NCOsup.- lisup.+A

[25] second amine molecule may be consumed by the proton liberated from carbamic acid forming carbamate.
1261 Rsub.2NIII ---> R2N112sup.
[27] Therefore for every carbon dioxide molecule, two amine molecules are used up. (2:1 ratio). Kinetically and thermodynamically this reaction pathway is generally favored for primary and secondary amines.
[28] Route 2 (proton accepting base Amine = CARBON DIOXIDE ,,, 1:1) 1291 A second reaction route for carbon dioxide absorption is carbon dioxide hydration to form bicarbonate. In this pathway an amine molecule simply acts as a proton accepting base for the hydration of carbon dioxide. The overall stoichiometry for this second pathway is [30] carbon dioxide + water ---> HCOsub3sup.- Hsup.+
[31] Rsub.3N Hsup.+ ---> Rsub.311sup.
[321 According to the route 2, one mole of amine is consumed per mole of carbon dioxide, so in terms of absorption capacity it is more efficient. For tertiary and some sterically hindered primary and secondary amities this is the only pathway contributing to absorption. However, this pathway is generally less favorable kinetically than carbamate formation.

[33] lithe earbamic acid formed is a weak. acid (higher pKa value) the extent of dissociation to form carbamate is low. Then the route 1 approaches a 1:1 carbon dioxide: amine molar stoichiometry because the carbamate does not deprotonate and consumes a second amine molecule.
What type of amines can have higher carbon dioxide absoiption capacity?
(1:1 carbon dioxide :amine ratio). This question was answered by Panay et al.
[34] Pauxty et at. have studied the carbon dioxide absorption capacity of 76 different amines. Among these, seven amines, consisting of one primary, three secondary, and three tertiary amines, were identified as exhibiting excellent absorption capacities. Following discussion is based on the publication by Pauxty et al.
[35] According to Palmy et at. the most interesting result is that all of these amines share a common structural feature, a hydroxyl group within 2 or 3 carbons of the amine functionality. While it is unclear what the role of this structural feature is, the distance of the hydroxyl functionality from the amine and the structural features around it appears crucial. For example, 2-piperidineethanol and 2-piperidinemethanol achieved capacities of near I, whereas 3-piperidinemethanol only achieved a capacity of 0.8. This

8 indicates that the proximity of the hydroxyl group and its freedom to move are important.
[36] According to Pauxty et al. one possibility is that a hydroxyl group the appropriate distance from the amine functionality, and with the appropriate structural features surrounding it, is able to form a stable intramolecular hydrogen bond with. the nitrogen to form a five or six member ring structure. Intramolecular hydrogen bond formation between amine and hydroxyl groups may decrease the.amine pKa, for primary and secondary amines it may also destabilize carbamate formation and push the absorption toward the more stoichiometrically efficient route 2.
[37] Therefore ionic liquids consisting of cations with hydroxyl groups at 2 or 3 carbon from amino groups have been synthesized.
[38] Flame Retardant ionic Liquids [391 Flame retardants for textile application have been reviewed by Weil and Levchik. They have provided historical details as well as current FR
treatments of textile fabrics. Some.of the common FR. treatments to fabrics are summarized below based on this review article. Most common FR
treatment of cotton fabrics is based on ammonium pyrophosphates. They impart self-extinguishing property to cotton fabrics. Borax is another

9 common flame retardant agent used on fabrics. These treatments are temporary due to their solubility in water.
[40] Polymers containing 35-45% bromine, poly(pentabromobenzyl acrylate) are used as a durable FR treatment on cotton and polyester fabrics. The FR property also can be improved by the addition of antimony oxide.
[41] In recent years, halogen-free, low smoke, and fume flame-retardant composites are becoming of increasing importance, because halogen-type flame retardants can cause problems, such as toxicity, corrosion, and smoke. This has promoted the development of halogen-free, flame-retardant materials. Prior efforts have shown that metal hydroxides are nontoxic and smoke-suppressing additives with a high decomposition temperature in flame-retardant polymeric materials.
[42] The FR material based on tetrakis(hydroxymethyl)phosphonium cation is the most widely sold commercial FR treatment product to date. It is generally agreed that ammonium and phosphonium salts have superior FR
properties.
[43] The above described PR treatments of fabrics are either non-durable or inefficient. Ionic liquids have excellent thermal stability and fire resistant properties. They are commercially available and also can be synthesized easily in an industrial scale.
[44] The burning process consists of heating from an external source, decomposition of fabric, combustion of flammable chemicals released from the burning fabric, and propagation of flame, [45] Burn process starts from an external source of fire. When sufficient heat is applied the fabric starts decomposing. The pyrolysis of fabric (cellulose) results in the release of Levoglucosan and its volatile combustible fragments such as alcohols, aldehydes, ketones, and hydrocarbons. These flammable chemicals burn and propagate the flame and generate more heat. This process petpetuates until the fabric is completely consumed by fire. Part of the decomposition products from the fabric also produce a carbonized residue (char) that does not burn readily.
The decomposition of cellulose can be expressed by the following equation:
[46] Cellulose 3 Flammable chemicals {II+ Char 14 (lincatalyzed burning) [47] A flame retardant alters (catalyzes) the decomposition path of cellulose so that the amount of flammable chemicals is reduced and the amount of char tbnned is increased.

f481 Cellulose 4 Flammable chemicals f4,) + Char In (Phosphonium catalyzed burning) [491 The ammonium and phosphortium flame retardants generally lower the decomposition temperature of cellulose and promote dehydration of the cellulose during -thermal stress. Phosphorus-containing compounds increase the amount of carbon .by redirecting chemical reactions involved in the decomposition. As more carbon is produced, the yields of volatile and flammable aldehydes and ketones are reduced. Ammonium based flame retardants also function through a similar mechanism.
[50] In general, nylon fabrics have low flammability than cotton fabrics.
Typical low weight nylon fabric melts and drips away, when exposed to flame and stops the propagation of flame.
[51] Nylon Cotton (NYCO) fabrics are made using a 50% nylon/50% cotton blend and provide combat utility uniforms with excellent. comfort and durability.. However, NYCO fabrics have no flame resistant (FR) properties. TherefOre for flame retardant fabrics one has to rely on expensive specialty fibers. Instead of using expensive fabrics, it will be economical to impart FR property on the NYCO fabric by treating them with flame resistant materials/coatings. The FR treatment should not deteriorate the fabric strength and should not add stiffness and significant weight to the fabric.
[52] ionic liquids containing ammonium and phosphonium cations exhibit exceptional flame resistant properties. In addition, they are non-flammable, high temperature stable (>250 degree C), non-volatile liquids and amenable to coating on textile fabrics. Unlike conventional FR chemicals, ionic liquids are generally colorless and do not interfere with the other properties of the military fabrics such as camouflage. Along with flame resistant property ionic liquids also have added advantage of multi-functional capabilities such as antistatic, conductive and antimicrobial properties. in spite of these excellent multifunctional properties, ionic liquids are not widely used in fabric treatment due to the lack of detailed studies on the ionic liquid coatings on textiles.
[53] Amino and hydroxy fimetional groups in the ionic liquid molecules can interact with the textile &ivies and can strongly bind to the fabric. This will increase the durability of the ionic liquids treated fabrics for several washings [54] ionic liquids as electrolytes and flame retardant additives to electrolytes in lithium ion batteries [55] Even though, enemy storage capacity of lithium ion-batteries is superior to other rechargeable battery chemistries, safety issues related with the lithium-ion batteries are the major hindrance for their application as high power batteries. The low boiling organic solvents used as the electrolytes are the main cause of the safety concerns. These solvents have a flash point around VC and could easily catch fire if vented from a hot battery.
Moreover, the electrolytes decompose on contact with the charged. active materials, both anodes and cathodes. At the end of the charging as well as at high temperatures, the cathode dissolves which accelerates the electrolyte decomposition. When a cell is heated above 13(re, exothermic chemical reactions between the electrolyte and electrodes trigger thermal run away reactions which are a serious safety hazard. Hence, high power lithium-ion batteries are developed with various external safety devices like current limiting devices, fuses, circuit breakers etc. These devices increase the cost and complexity of the battery module and also consume substantial power.
[561 Considering these safety hazards, development of non-flammable, low volatile, thermally as well as electrochemically stable lithium battery electrolytes are essential for the use of high power lithium batteries in aviation. In this context, "ionic liquids" (ILs) which are liquids at room temperature composed of ions as the electrolytes fbr high power lithium batteries look extremely attractive. Pyrrolidirtium based room temperature ionic liquids have been widely investigated as electrolytes in lithium batteries because of their low viscosities and reasonable conductivities.
These ionic liquids are 'non-flammable' chemicals but are not 'flame-retardants'. Uncontrolled thermal reactions in high-energy density lithium batteries may lead to .fire and pyiTolidinium based ionic liquids cannot withstand these extreme conditions. This scenario undercuts the original reason for employing ionic liquids as electrolytes even by compromising on their low conductivity compared to organic carbonate based electrolytes.
Therethre, alternate ionic liquids need to be developed which exhibit high ionic conductivity and non-flammability and are capable of quenching the fire in case of short circuits, local heating and or in abuse conditions such as overcharging.
1571 Ionic liquids for corrosion protection 1581 Ionic liquids as desiccants and chloride removal system- Corrosion is a critical problem for the aircraft& it costs Department of Defense over $10 billion year just in maintenance of equipment's and installations.
Corrosion is not only a cost issue, but it also impacts our troop's readiness, safety and their pertbrmance. The effect of corrosion felt by the Air Force most because aircraft structures are mostly made of metal. Corrosion is usually battled with special alloys and a variety of corrosion protection coatings. However, there is no 'silver bullet' available to completely eliminate the corrosion problem. The corrosion issue can be alleviated if the environmental factors that hasten the corrosion of metal alloys can be addressed properly. Two important factors that affect metals in an aircraft are humidity and Chloride content in the atmosphere. Currently humidity level in an aircraft is controlled with the help of dehumidifiers. However, chloride deposition on the aircraft parts requires special attention. Because, desiccants used in the humidity control system are not effective against chloride accumulation. 'Therefore, new efficient desiccants that not only dehumidify the environment but also remove chloride ions from air are needed.
[59] Ionic liquid based desiccant systems are capable of both humidity control and chloride removal. Ionic liquids are non-volatile liquids as well as efficient desiccants. The ionic liquids can be functiomdized to remove chloride ions from the environment.
[60] It will be readily understood by the skilled artisan that numerous alterations may be made to the examples and instructions given herein.
These and other objects and features of present invention will be made apparent from the tbllowing examples. The following examples as described are not intended to be construed as limiting the scope of the present invention.

SUMMARY
[611 Disclosure provided an ionic liquid represented by the structure of the following Formula l;

--(Cf-14-----X A-m [621 Formula 1 L631 wherein 1641 (a) R. and Ware each independently U. or a Ci to 02 straight-chain alkyl group or branched alkyl group or aryl group, [651 (b) .m is an integer I to 6, [661 (c) X is ¨WR3)-(0-12)(1--OH, wherein R3 is H or Ci to G straight-chain or branched alkyl group and q is an integer from 2 to 4, and [67] (d) A isan anion selected from the group consisting of 1B1:41", [PF61-, [C113CO2.1", [1-IS041", [CF3S031 = , 1(CF.3$02)2N]= R(73502)3(1, [SO4 Cr, Br, I. [N(CN)2] -", l(1)04)(C41-1021-, ((.1)04C2I15)21-, [(1)04 Xci)fi 3 )2r, [cH3cH2osc3t- [cH3ocozr and amino acid.
[68) Disclosure provides a fire retardant coating ibr textile fabrics.
The fire retardant has the ionic liquid of Formula 1. Disclosure provides a solvent for carbon dioxide capture. The solvent includes the ionic liquid of Formula I Disclosure provides an electrolyte in a lithium ion battery. The electrolyte includes the ionic liquid of Formula .1. Disclosure provides a flame retardant additive to an electrolyte in a lithium ion battery. The flame retardant additive includes the ionic liquid of Formula 1. Disclosure provides an electrolyte in a metal air battery. The electrolyte includes the ionic liquid of FormUla 1. Disclosure provides a name retardant additive to an el-ectrolyte=in a metal air battery. The flame retardant additive includes the ionic liquid of Formula I.
[691 Disclosure provides an ionic liquid represented by the structure of the foll OW ifig Formula 2:

.....X
A-170] 1-4,rmuta 2 17 l.

wherein 17211 (a) R and R2 are each independently I-1, or a CI to C12 straight-chain alkyl group or branched alkyl group or aryl group, 1731 (b) m is an integer I to 6, [741 (c) X is ---N(R3)-(0-12)q-OH, wherein R3 is H. or C to C6 straight-chain or branched alkyl group and q is an integer from 2 to 4, and, is [75] (d) A-- is an anion selected from the group consistilw; of [BEd-, [CH3CO2]-, [HAM ICF3$0,3]-, [(CF3S02)2N1--, [(CF3$02)Cr [S0412-, Cl- ,Br, [N(CN)2] [ 04C4119 )21, IS( P 4).(C! , PO4 XCa-102r [C113e1120$031-,[0j30(1701]--- and amino acid.
[76] Disclosure provides a fire retardant coating for textile fabrics, The fire retardant includes the ionic liquid Of Formula 2. Disclosure provides a.
solvent :for carbon dioxide capture. The solvent includes the ionic liquid of Formula 2. Disclosure provides an electrolyte in a lithium ion battery. The electrolyte includes the ionic liquid. of Formula 2. Disclosure provides a flame retardant additive to .an electrolyte in a lithium ion battery. The flame retardant additive includes the ionic liquid of Formula 2. Disclosure provides an electrolyte in a metal air battery. The electrolyte includes the ionic liquid of Formula 2. Disclosure provides a flame retardant additive to an electrolyte in a metal air battery. The flame retardant additive includes the ionic liquid of Formula 2, 171 Disclosure pros ides an ionic liquid having a flame retardant property, The ionic liquid is represented by Formula 3:

m \
1781 Formula 3 [79] wherein [801 (a) and 112 are each independently H, or a CI to C12 straight-chain alkyl group or branched alkyl group or aryl group, [81] 0)) m is an integer 1 to 6, [82] (c) Z is -OH or NR3R4, where R3 and R.' are each independently H or CI to C6 straight-chain or brandied alkyl group, and, [83] (4) A" is an anion selected from the group consisting of [BF4]-, [My, [C113CO2] [11SO4] ", [CF3S03]", R.c.F3so2)2Nit,Rcr3so2)3ertsso412-.
Cl. Br ,11"-, [N(CN)2] [(PO4)(C41.19)21-, [(1)04)(C2H5)21-, l(PO4)(Chil)irs [C11301:20S031, [CF1300O21 and amino acid, and wherein the ionic liquid has flame retardant property.
[84] Disclosure provides a fire retardant coating for textile fabrics. The fire retardant coating includes the ionic liquid of Formula 3. Disclosure provides an electrolyte in a lithium ion battery. The electrolyte includes the ionic liquid of Formula 3. Disclosure provides a flame retardant additive to an electrolyte in a lithium ion battery. The flame retardant additive includes the ionic liquid of Formula 3. Disclosure provides an electrolyte in a metal air battery. The electrolyte includes the ionic liquid of Formula 3. Disclosure provides a flame retardant additive to an electrolyte in a metal air battery. The flame retardant additive includes the ionic liquid of Formula 3.
[85] Disclosure provides a method of preparing the ionic liquid of Formula 1. The method includes refluxing the compound having Formula 4 with an ammo alcohol and potassium carbonate in the presence of a solvent to obtain the ionic liquid of Formula 1. Formula 4 is represented by the following structure RI
i ,..( 1-----hi A--21m [86] Formula 4 [87] wherein [88] (a) R, and R2 are each independently H, or a CI to C12 straight-chain alkyl group or branched alkyl group or aryl group, [89] (b) m is an integer I to 6, [90] (c) H is Cl. Br, I.
[91 j (d) A- is Cl , Br, I-[92] Disclosure provides a method of preparing the ionic liquid of Formula 2, The method includes refluxing the compound represented by the Formula 5 with an amino alcohol and potassium carbonate in a solvent to obtain the ionic liquid of Formula 4. Formula 5 is represented by the thilowing structure A-+ hi l93] Formula 5 [94] wherein [95] (a) R j and 1Z2 are each independently H, or a Ci to C12 straight-chain alkyl group or branched alkyl group or aryl group, [96] (b) m is an integer Ito 6, [97] (c) H is CI, Br, L and, [98] (d) A. is Cl", Br, r .
[99] Disclosure provides a flame retardant fabric product having a fabric, a flame retardant ionic liquid represented by Formula 3, and a binder. About 1% to about 60% by weight of the flame retardant fabric product is made up of the flame retardant ionic liquid. The fabric can be Cotton, Cellulose, Rayon, Nylon, Polyester, Polyurethane Poiyamideõ and aramid.

[100] Disclosure provides a method of preparing the flame retardant fabric.
The method includes coating the fabric with the flame retardant ionic liquid represented by Formula 3 and the binder to obtain a coated fabric. The coated fabric is cured at a temperature of about 20 degree C to about 300 degree C tbr about 1 minute to about 12 hours to obtain the flame retardant fabric.
BRIEF DESCRIPTION OF THE DRAWINGS
[101] The above objectives and advantages of the disclosed teachings will become more apparent by describing in detail preferred embodiments thereof with reference to the attached drawings in which:
[102] Figure 1. Chemical structure of typical cations and anions of ionic liquid.
[103 Figure 2. Chemical structure of representative ionic liquids containing ammo alcohol filmdom' groups.
[104.1 Figure 3. Proton nmr spectrum of Formula 8 [105] 'Figure 4. Proton runr spectrum of Formula 9 [106] Figure 5. Proton unit- spectrum of Formula 10, the product from the reaction between bromopmpyl-methyl imidazole and N-methyl ethanolainine.
[107] Figure 6, C-13 NMR spectrum of Formula 10 [108] Figure 7. Proton nmr spectrum ofFomula ii (Bromopropyl-dimethyl imi(azolium bromide) [1091 Figure 8, Proton NNW spectrum of Formula 12 11101 Figure 9. C-13 N11,111 spectrum of Formula 12. NMR resonance peaks from acetonitrile solvent is marked in the Figure.
[1 I] Figure 10. Proton mar spectrum of Formula 13 [112] Figure 11. Proton rimr spectrum of Formula 14 [113] Figure 12. Proton n mr spectrum of Formula 15 [114] Figure 13. Proton tunr spectrum of Formula 16 [115] Figure 14. Proton iimr spectrum of Formula 17 [1161 Figure IS. Thermogravimetric analysis (TGA) plot of formula 7 under the flow of nitrogen and 20% oxygen [1171 Figure 16. CO2 absorption by amino alcohol funtionalized ionic liquids in comparison with hexyl methyl imidazolitun bis(trifluoromethyl sulfonypimide ionic liquid (C6miniNTf2) 11181 Figure 17, Overlay piot of TGA data of uncoated-NYCO fabirc and 'MOP coated NYCO fabric [119] Figure 18. Proton 'NAIR spectrum of TBAP-.DBP ionic liquid 11201 Figure 19. P-31 NMR spectrum of TBAP-DBP ionic liquid [121] Figure 20. Vertical flame test data of "'BAP-Dili> based flame retardants as a function of urea addition [122] Figure 21. Comparison of flame retardant property as function of anions [123] figure 22. Pictures of the flammability of dimethylcarbonate (DMC) and fire-quenching effect of the phosphoni.um ionic liquid, TBAP-Br.
DETAILED DESCRIPTION
[124] It is an object of the present disclosure to provide amino alcohol functionalized ionic liquid compounds, compositions together with methods for their synthesis and their use.
[125] It is an object of the present disclosure to provide an ionic liquid with structural moiety consisting of a hydroxyl group or hydroxyl groups within 2 or 3 carbons of the amine functional group.
[1261 It is an object of the present disclosure to provide an ionic liquid of Formula 1:
_________________________________ X A
m Formula [127] wherein [128] (a) R1 and le are each independently II, or a CI to C12 straight-chain alkyl group or branched alkyl group or aryl group, [129] (b) in is an integer I to 6, [I30] (c) X is --N(R3)-(CH2)1-011 where R3 is H or C1 to C6 straight-chain or branched alkyl group and q is an integer from 2 to 4, and.
[131] (d) A-- is an anion selected from the group consisting a [13F4, [CH3CO21 [USN [CF3S03], [(CF3S0.1)2Nr, [(CF3S02)3Cr. [S0412-, Cl-, Br, I", [N(CN)2] ", [(PO4)(C4H9)21-, [(PO4)(C2H5)2r, RP04.)(Q115)2.1", [Cilla2OSOA",[C113(X:02j- and amino acid.
[132] Disclosure provides a fire retardant coating for textile fabrics. The fire retardant has the ionic liquid of Formula. I. Disclosure provides a solvent for carbon dioxide capture. The solvent includes the ionic liquid of Formula I. Disclosure provides an electrolyte in a lithium ion battery. The electrolyte includes the ionic liquid of Formula I. Disclosure provides a flame retardant additive to an electrolyte in a lithium ion battery. The flame retardant additive includes the ionic liquid of Formula 1. Disclosure provides an electrolyte in a metal air battery. The electrolyte includes the ionic liquid of .Formula I. Disclosure provides a flame retardant additive to an electrolyte in a metal air battery . The flame retardant additive includes the ionic liquid of Formula 1.
[1331 It is an object of the present disclosure to provide an ionic liquid represented by the structure of the Formula 2:

4_ in X A
\
Formula 2 [134] wherein 11351 (a) Rj and .17k2 are each independently H, or a Ci to C12 straight,chain alkyl group or branched alkyl group or aryl group [136] (b) tn is an integer 1 to 6 [137] (0 X i...-11+4(K.31)-(CHz)g-OH wherein "W is H or CI to C6 straight-chain or branched alkyl group and q is an integer, from 2 to 4; and 1138] (4) A" is an anion selected from the group consisting of [I3F4". [PF'4", [CHA7.02]--, [H SO4] [CF3S03Y, [(CF3S02)2N]-, [(cF3S02)3C1-, [SO4}.
CI", Br. EN(CN)21-, [(PC/4)(C41021T, 1(PO4)(C2t15)2.1-. [(1)04)(C6H5)21-, [CI-I3CII.20S03]-, [C[130(1'1)21- and amino acid.
11391 Examples of include but not limited to monoethanot amine, diethanol amine. N-methyl ethanolamine 2,amino-2-metby1-1,3-propauedicit, 2-pi peridineethanol, 2-piperidinemethanol, diisopropauol amine, 3-quinuclidinol,.NN-diillethylethanolatnine, and 3-piperidino- I,2-propandiol groups.

[1401 It is an object of the present disclosure to provide a solvent composition containing a mixture of amtne timetionalized ionic liquids with alcohol functional ized ionic liquids.
[1411 It is an object of the present disclosure to use functionalized ionic liquids as sol vents for carbon dioxide capture.
11421 It is an object of the present disclosure to use functionalized ionic liquids as fire retardant coating on articles including textile fabrics.
[1431 It is an object of the present disclosure to use innctionalized ionic liquids as desiccants to remove moisture and chloride and other corrosive chemicals.
[1441 It is an object of the present disclosure to use functionalized ionic liquids as solvents in organic reactions.
[1451 It is an object of the present disclosure to use functional ized ionic liquids as electrolyte in metal batteries including lithium ion batteries, and metal air batteries.
1146.1 It is an object of the present disclosure to use functionalized ionic liquids as additive to electrolyte in metal batteries including lithium ion batteries, and metal air batteries.
11471 it is an object of the present disclosure to use functionalized ionic liquids as a medium for electrodeposition of metal coating including nickel and cobalt coatings.

[1481 it is an object of the present disclosureto use functionalized ionic liquids as a solvent or medium for coating powders.
[1491 .11t. it an object of the .present disclosure to use .funclimalized ionic liquids as. a solvent or medium for preparing nano powders including nano.
metal powders and nanometal oxide powders.
501 it is an object of the present disclosure to use functionalized ionic liquids as a scrubbing material for de.sulfuriza.tion.
[151.1 Disclosure .provides a fireretardant coating for textile fabrics. The fire retardant includes the ionic liquid an-mm.11a 2. Disclosure .provides a solvent for carbon dioxide capture. Ilu....solvent includes the ionic liquid of Formula 2. Disclosure provides an electrolyte in a lithium ion battery. The electrolyte includes the ionic liquid of Formula 2 Disclosure provides a.
flame retardant additive to an electrolyte in. a lithium ion battery.. The flame retardant additive includes the ionic liquid of Formula .2.. Disclosure provides an electrolyte in.a metal air battery. The electrolyte includes the ionic liquid of:Formula 2. Disclosure provides a flame retardant additive to an eieetrollytein a metal air battery. The flame. retardant additive includes the ionic liquid of Formula .2.
1152.1 It it an object of the present disclosure to use an ionic liquid represented by .the structure Formula 3. of the as a flame retardant compound.

+.õ..(CHAir..z A--R Formula 3 [153] wherein [154] (a) and 112 are each independently H, or a CI to C12 straight-chain alkyl group or branched alkyl group or aryl group [155] (b) m is an integer 1 to 6 [156] (c) Z is -014 or NR3R4 wherein R3 and R4 are each independently H or CI to C6 straight-chain or brandied alkyl group [157] (4) A" is an anion selected from the group consisting of [BEd-, [Mt, [CH3CO21 [11SO4] ", [CF3S03]", R.c.F3so2)2Nit,Rcr3so2)3er1s0412-.
Br-, I-, [N(CN)21 [(PO4)(C4149)2]-, [(1)04)(C2H5)21-, RP04)(C61102..r.
[CH3CH/OSO31, [CH300O21" and amino acid, [158] Disclosure provides a fire retardant coating for textile fabrics. The fire retardant coating includes the ionic liquid of Formula 3. Disclosure provides an electrolyte in a lithium ion battery. The electrolyte includes the ionic liquid of Formula 3. Disclosure provides a flame retardant additive to an electrolyte in a lithium ion battery. The flame retardant additive includes the ionic liquid of Formula 3. Disclosure provides an electrolyte in a metal air battery: 'll'he electrolyte includes the ionic liquid of Formula 3. Disclosure provides a flame retardant additive to an electrolyte in a metal air battery. The flame retardant additive includes the ionic liquid of Formula 3.
[159] it is another object of the present disclosure is to provide a method of preparing the ionic liquid represented by the formula 1. The method includes refluxing the compound represented by the Formula 4 with an amino alcohol and potassium carbonate.

'N H A-. \N+

a H ) 2. m , [1601 'Formula 4 H61] wherein [162] (a) R' and R2 are each independently El, or a Ci to C.12 straight-chain alkyl group or branched alkyl group or aryl group [163] (b) this an integer] to 6 [164] (C) '11: is C.1,13r, I
[165] (d) A is Cl, tir--,:r. .
[166] it is another object of the present disclosure is to provide a method of preparing the ionic liquid of claim 8. The method includes refluxing the compound represented by the Formula 5 with an amino alcohol.

4m-----1-1 \ 1 Formula 5 [167] wherein [168] (a) RI and le are each independently H. or a Ci to C12 straight-chain alkyl group or branched alkyl group or aryl group [169] 0) in is an integer] to 6 [170] (c) H is CI, Br, I
[171] (d) A' is Cl". Br, .1.". .Refluxing also requires potassium carbonate.
[172] Carbon dioxide capture by functionalized ionic liquids [173] There is increasing concern for the reduction of CO2 emissions from flue and fuel gas operations because these emissions have resulted in global climate change and a significant increase in global warming due to the "greenhouse gas (GE1G) effect". Approximately 83% of the GHG
emissions in the U.S. are produced from combustion and mallet uses of fossil fuels. One approach that holds great promise for reducing GIIG
emissions is carbon capture and sequestration (CCS). Under this concept.
CO2 would be captured from large point sources, such as power plants, and injected into geologic formations. This approach would lock up (sequester) the CO2 for thousands of years. DOE's Carbon Sequestration Program that is managed by the National Energy Technology Laboratory (NEIL), is pursuing various technological approaches aimed at reducing GM
emissions.
[174] Aqueous amine Absorption is the state-of-the-art technology that is used to separate and capture CO2 from flue gas streams produced by existing coal-fired electric generating power plants. However, the use of amines for CO2 absorption has some disadvantages, including (i) high energy requirement for solvent regeneration, (ii) their high vapor pressure and subsequent mass loss through evaporation, (iii) degradation of the solvent and associated plant corrosion, and (iv) significant-capital and operating costs. On the other hand, solvent regeneration is easier and less energy intensive with physical adsorption of CO2. Physical absorption has generally lower absorption capacity when compared to chemical absorption under low CO2 partial pressures.
1-175.1 The concept of using ionic liquids (IL's) as potential alternatives to aqueous alkanolamines for CO2 capture has recently gained considerable interest. IL's have advantages that include negligible vapor pressure, higher thermal stability and lower heat capacity in addition, like alkanolamines they have fast capture kinetics and low viscosity. In order to take.

advantage of the useful properties of 1L's for post-combustion CO2 capture, functionalized-IL's to be investigated as potential replacement solvents for aqueous amine scrubbing systems.
[176] This disclosure provides routes for synthesizing amino-alcohol functionalized ionic liquids and evaluated their CO2 capture capacity and regeneration capability. The amino-alcohol functionalized ionic liquids exhibited 20X higher CO2 capture capacity compared to unfunctionalized IL's at low pressures (I bar). The IL's also demonstrated high thermal stability both in nitrogen and in air. CO2 can be thermally desorbed by heating the IL's to 80-120 degreeC at I bar CO2 pressure without significant degradation. The cost and energy performance calculations clearly demonstrated that the IL's disclosed here could be competitive with an amine process if the target parameters such as CO2 capture capacity, viscosity, heat capacity, and cost of the IL are achieved.
[177] The selection of a suitable solvent is vital for the economic viability of the M2-capture process. The main selection criteria are high solubility of carbon dioxide and, equally important, high Absorption selectivity of carbon dioxide over nitrogen. Furthermore, low energy desorption is highly desirable, as it reduces the necessary regeneration temperature and pressure difference. hi order to prevent the loss of solvent, a low vapor pressure and high thermal stability as well as long-tenn stability are beneficial. The cost and environmental toxicity of the solvents have to be considered along with the evaporative loss and chemical degradation characteristics of [Ls.
[1781 carbon dioxide absorption data showed that mixing of amino and hydroxy functionli zed ionic liquids exhibit higher carbon dioxide absorption. .I.herefore, synthesizing new ionic liquids containing both hydroxyl and amino groups in a single ionic liquid molecule will result in a better carbon. dioxide capturing solvent.
l.79 In this disclosure ionic liquids :incorporating qructural features:, that hydroxyl group within 2 carbons of the amine functionality, have been synthesized and their CO2 absorption capacity was measured. A maximum of mu! (1:02/mol IL ratio of 0.4 was obtained. It was observed that subtle changes in the chemical structure could affect the CO2 absorption capacity:
For example, by replacing methyl inlidazolium with dimethyliinidazolium moiety, the CO2 absorption capacity of II.:s increased by ¨50%.
[MI Synthesis of ionic liquids containing amino-alcohol functional groups [181] A simple and versatile two step path way was developed for synthesizing ionic liquids containing cations with both alcohol and amino functional groups. In the first step bromoalkyl precursor compound of alkyl imidazok or alkyl phosphine was synthesized. For example, methyl imidazole was reacted with 1,3 dibromopropane to from bromopropyl methyl imidazolium bromide as represented in the scheme below:
CH3 Br--8( 11821 This synthesis process was very versatile in that bromoalkyll imidazotium and bromoalkyl phosphonium precursors can be reacted with any type of alkanol amine compounds to form the corresponding amino alcohol functionalized ionic liquids. For example, reaction with N-tnethyl ethanolamine is provided below:
Br : Br' nõc-[1831 The above synthesis process IS simple to scale up. This process Can be extended to other types of amino alcohols without any drastic modifications in the reaction conditions.. The bromo anions were ion-exchanged with various anions listed in Figure I to form the corresponding ionic liquids.
[184] The chemical structure atypical ionic liquids containing cations with amine and alcohol functional groups are provided in Figure 2.
[ 1 851 Thermal stability of Ionic Liquids 11861 In order to determine the thermal stability of the funetionalized itnidazolium ionic liquids synthesized in the thermogravimetric analysis (MA) was conducted. The purge atmosphere was either nitrogen or air at 100 milmin and 10/min to 600 C. Typical .FGA data under nitrogen and air (20% Oxygen) are provided in Figure 15. It is important to note that the amino alcohol groups are stable up to 280 C. This stability cannot be achieved by the physical mixing of nionoethanol amine (MIA) with an unfttnctionalized ionic liquid. Both the curves almost overlap indicating that the disclosed ionic liquids are stable in nitrogen as well as in air up to 280QC, [187] Carbon dioxide Absorption Studies [1881 CO2 absorption setup was designed and built in-house to measure the amount of CO2 absorbed by the various IL samples of this disclosure.
The ionic liquid samples (about 3 g) were loaded in the isochoric cell and degassed at 809C and 3 mbar vacuum for a period of 12-18 h. After cooling the sample to 25 C, CO2 gas was introduced into the isoehoric cell. The desired pressure was set at between 0-8 bar. The sample was stirred during the absorption experiment. The weight iiierease due to CO2 absorption was measured at various exposure times and pressures and plotted in Figure 16, The total absorption duration was 18 blur all the samples tested. Even after exposing for 18h, the equilibrium may not have been reached with these ionic liquids due to the slow reaction kinetics and the high viscosity of the solvent, in Figure 16, CO2 absorption data of funetionalized (cheinisoiption) and 1-hexyl-3-methyl imidazolium bis(trifl uoromethyl sulfonypimide (C6miniNIt2) (physisorption) are compared.
[189] Viscosity [190] Upon CO2 absorption of the viscosity of all of these ILs has increased.
But the increase in viscosity is marginal compared to the anion functionalized ionic liquids reported by Brennecke et al. For example, Amine-Functionalized Anion-Tethered IL's based on trihexyl(tetradecyp phosphonium systems exhibited a viscosity increase of 48-240 folds compared <2 fold increase in the amino alcohol functionalized cation ion-tethered systems disclosed here. These results indicate that anion-functionalized IL's exhibit more effect viscosity upon CO2 absorption than cation-functionalized IL's. The viscosities of cation-ftinctionalized disclosed here can be decreased by selecting appropriate anions.
[191] Desorption data [192] Ionic liquid represented by theformula 17 was down selected for investigating the stability of CO2 absorption during the recycling of IL.
CO2 absorption was carried out at 40 C for 12 h under 0.15 bar CO2 pressure, and desorption was performed at 80-120 "C under 1 bar CO2 pressure for 30 minutes. These are the typical conditions used in the industrial CO2 scrubber. The absorption capacity of IL remained stable during 15 cycles (100 plus Or minus 2 14) indicting that the CO2 absorption is reversible..
11931 Most of the studies on N1T2 anion-based IL's were focused on CO2 capture by physisorption mechanism. Based on molecular simulations, it has been suggested that the anions surround the amino groups in the 11...s and shield them from reacting with CO2, The bulky NTf2 can be substituted with smaller anions such as BF4 or PF6 or amino acid anions which may not hinder the reaction between arnino-alrohot groups and CO2 molecules. :1314 anion containing amino functionalized 1:1:, also known to exhibit higher CO2 absorption capacity.
[1941 The following is the summary of the CO2 absorption data observed:
[195] 1. A Mino-alcohoi funetionaliziA ionic liquids show higher CO2 absorption capacity (20X) than the unfunctionalized 1112s (C6miniNTf2) at low CO2 pressures bar).
[1961 2. The absorption of CO2 by ionic liquids represented by the chemical formulae 14, 15, 16 and 17, even at low CO2 pressures (<1 bar), indicates that CO2 is absorbed via a chemisorption mechanism.
[197] 3. Dimethyl imidazolium IL's exhibit 2X higher absorption capacity compared to monomethyl imidazotium IL's. This shows even minor modifications in the chemical structure can strongly influence the CO2 absorption property of the IL's.

[198] 4. Anions form strong hydrogen bonds with amino groups and organize around the amino-alcohol groups. So, high reactivity and absorption capacity can be achieved by using a different anion which is not hindering the interaction between CO2 molecule and amino-alcohol groups.
[199] 5. High viscosity of the ftmctionalized IL's. before and after CO2 capture. is one of the major hurdles in implementing these IL's in the post combustion C;02 capture process. Viscosity of functionalized IL's decreases with the reduction in the number of protons in the amino group (NH2(10,000 cl)) >NH (4435 el)) >N-CH3 (407 01))). Substitution of N-C2115 or N-aliphatic ring for N-H group can help in reducing the viscosity of the IL without decreasing the CO2 absorption.
[2(101 6. Dilution of functionalized IL's with low viscosity IL solvent is a viable alternative method to alleviate the viscosity problem.
[201] 7. The absorption capacity of IL remained stable over 15 cycles of CO2 absorption/desorption indicating reversibility of functionalized [202] Flame retardant ionic liquids [2031 This disclosure provided the several ionic liquids based on imidazolium cations and phosphonium cation. Interestingly these ionic liquids exhibited .flame retardant (referred in this disclosure as "FR") properties. These ionic liquids are coated onto textile fabrics including but not limited to cotton, nylon, nylon:cotton (50:50) (here onwards refered as 'NYCO"), polyester, polyethylene, polypropylene, polyurethane, for imparting flame retardancy to the fabrics. Durable FR coating can be formed by chemically reacting or physically containing on the surface of the fabric ['LA. Perenich, Protective Clothing: Use of Flame-Retardant Textile Finishes, Ch. 7, Protective Clothing Systems and Materials, Ed. By M. Raheel, Marcel Dekker, (1994)1.
12041 These coatings are not removed during repeated washings of at least 1 times preferably up to at least about 25 washings. The FR coatings are typically applied by pad-dry-cure process from the formulations containing FR chemical (ionic liquid in this case) and finishing chemicals such as cross-linking agents.
[2051 The FR coating formulation were applied on to the fabric by the following two approaches: (a) Applying directly onto the textile fabric or by using a binder including but not limited to melamine, urea, acrylate, polyurethane, epoxy, polysiloxane, and silane based binders. Simple ionic liquids based on imidazolium or phosphonium cations with appropriate binders were added to the FR coating formulation for better cross-linking of the ionic liquids to fabrics. (b) Second approach was to strongly bind ionic liquids to fabric is using insitu-polymerization to strongly bind around the fibers of the fabric. For insitu-polymerzation, monomers such as Acrylamido-2-propane-sulfonic acid (AMPS) with cross-linker N,V-Methylene bisacrylamide (MB.Am) were mixed with ionic liquids in the coating formulation.
[206] Two ionic liquids tetrabutyl phosphonium diethyl phosphate (TPEP) and Ethyl 'methyl imidazolium diethyl phosphate (EIP) were purchased from IoLiTec Mc., Tuscaloosa, AL Acrylamido-2-propane-sulfonic acid (AMPS), cross-linker N,N*-Methylene bisacrylamide (MBAm). Tributyl phosphine, Triethyl amine (TEA), and 1-bromo propanol were purchased from Sigma Aldrich, Saint Louis, MO. Solvents such as acetonitrile, ether, and methanol were purchased from Phamm Aaper, Belmont, NC. 419W
style cotton fabric was purchased from Test Fabrics, West Pittston, PA.
Rip-stop weave Nylon 50: Cotton 50 fabrics were supplied by the Brittany Dyeing and Printing Corporation, New Bedtbrd, MA.
[207] Flame resistance of two ionic liquids tetrabutyl phosphonium diethyl phosphate (TPEP) and Ethyl methyl imidazolitun diethyl phosphate (E1P) coated 419W cotton fabrics were measured according to standard test method ASTM 6413-08. The uncoated cotton control fabric- was completely consumed by the fire during the test. The ionic liquids TPEP
and EIP coated cotton fabrics formed char during flame testing. But it also exhibited higher char length. Their char yield and char length were very high as shown in Table 3 provided in the example 19. The ionic liquids themselves are non-flammable materials but when coated onto cotton .fabric they did not protect the fabric from fire. Mixing these two ionic liquids with urea also resulted in poor char yield (less than 42 percent).
[208] Polymerization coating with AMPS
[209] In order to improve the flame retardant property, the 11TP-coated cotton fabric was coated with a layer of AMPS (30%) monomer and MBAm (3%) cross linker. Then the fabric was air dried for 4 days before the vertical flame testing. Cotton fabric coated with TPEPIAMPS-MBAm was subjected to vertical flame testing. The coated fabric exhibited a less vigorous flame than the uncoated control fabric. After-flame time and char length was also significantly reduced and no afterglow was observed.
[210] The various compositions of AMPS/MBAni polymer coatings gave a clear indication of how effective the coating becomes with different ratios of the monomer and cross linking agent. The lowest char length and highest char yield were Observed for the samples coated with a 30% AMPS/6%
MBAm solution, with ammonium persul fate (APS) to catalyze polymerization (Table 4), Because of the dynamic nature of the flame test, these two metrics (char length and char yield) must be examined together in order to determine performance level of a given coating. This specific solution composition excels in both areas, indicating its suitability as a FR
coating on cotton fabrics.

211] With the ideal AMPS,IMBAm composition determined, the combination of AMPS polymer with an ionic liquid was tested. Results (Table 5) indicated that while layer by layer deposition of polymer and ionic liquid coatings produce better properties than combining the two in one solution, the final coatings are not as effective as the polymer solution on its own. This can be attributed, perhaps, to the ionic liquid interfering with the formation of a polymeric network, thus reducing its ability resist flame. The presence of the ionic liquid does provide a smoother and more .flexible fabric after coating, but pertbrmance was not satisfactory for these coatings.
[212] Disclosure provides a flame retardant fabric product having a fabric, a flame retardant ionic liquid represented by Formula 3, and a binder. About 1% to about 60% by weight of the flame retardant fabric product is made up of the flame retardant ionic :liquid. The fabric, can be Cotton, Cellulose, Rayon, Nylon, Polyester, Polyurethane Polyamide, and Aramid.
[213] Disclosure provides a method of preparing the flame retardant fabric.
The method includes coating the fabric with the flame retardant ionic liquid represented by Formula 3 and the binder to obtain a coated fabric. The coated fabric is cured at a temperature of about 20 degree C to about 300 degree C for about 1 minute to about 12 hours to obtain the flame retardant &bric.

[214] AMPS coating on NYCO fabric [215] 50 Nylon 50 Cotton Universal ripstop fabric class 6 MIL-DTL-41443613 pure finish (NYCO) fabric was coated with AMPS. The AMPS FR
formulation optimized for cotton fabric was used in coating NYCO fabric, Vertical flame test was conducted on AMPS-coated 'NYCO fabric. AMPS-coated NYCO fabrics performed poorly under vertical flame testing. This result was unexpected because AMPS coated cotton fabrics exhibited excellent flame retardant behavior. Probably AMPS has less interaction with Nylon fibers compared to cotton fibers.
[216] litydroxy fulletionalized phosphonium ionic liquids: Tributyl hydroxyl propyi phosphonium cation containing ionic liquids [217] I lydroxy propyl tributyl phosphonium bromide, here after referred as 17130P-Be or as 'Formula 20 in this disclosure was synthesized by reacting tributYlphosphine, [Bu3P] with bromo propanol (Example 22).
The chemical structure of '1110P-Br' is provided below.

HC
CH.

[218] TBOP, when combined with urea, demonstrated excellent flame retardant property on a NYCX) fabric. Vertical flame test results are provided in Table 6. Although TBOP by itself did not function well as a flame retardant coating, the combination of this liquid and urea gave results better than 'REP and Ell P ionic liquids. The interaction of TBoi) and urea is most likely similar to the tetrakis hydroxyl methyl phosphonium chloride salt (THPC) (commercially available under the trade name. Pyrosant), due their similar chemical structures.
[219] When paired with other fabric binders such as Knittex(' from Huntsman, the fabric performed similarly on vertical flame testing. A
combination of Titanium (IV) oxide and TEOS added to the MOP/urea mixture provided results similar to those of pure TBOP/urea, although the fabric had a white tint from the TiO2 powder.
[220] Thermogravimetric analysis (TGA) can be helpful in deducing the decomposition mechanism of flame retardant coated fabric. Therefore, the thermal degradation behaviors of uncoated NYC() (control) and MOP/Urea coated NYC() fabrics were analyzed using TGA. High thermal stability of TBOP ionic liquid is clearly demonstrated by the TGA curve provided in Figure 15. The initial decomposition temperature of MOP is about 290 degreee. Thermal decomposition of NYCO fabric in air occurs in two stages. The first stage decomposing temperature of uncoated-NYCO

fabric is 342 degreeC corresponds to the decomposition of cotton in the NYCO fabric. This decomposition temperature is shifted to 311 degreeC by the phosphonium catalyzed decomposition of cotton. This behavior is similar to the behavior of THPc flame retardant material. But. the. initial decomposition temperature of TIIPC is around 1.84 degreeC compared to 311 degreeC for TBOP indicating the relatively higher thermal stability of mop. The second stage weight loss is centered around 446 degreeC is due to the decomposition of Nylon material in the M.7C0 fabric. This decomposition temperature is also decreased in the TBOP-Britirea coated NYCO fabric. This indicates that hydroxyl or amine ftmtionalized phosphonium ionic liquids interact, with both cotton and nylon fibers, of the NYCO fabric. Therefore, hydroxyl or amine functionaliml phosphonium ionic liquids can be used as -FR coating on both 100 percent cotton fabric and 100 percent nylon fabric. The residue from sample TBOP-BriUrea coated fabric was a rigid black solid with the original sample form and fabric weave patterns visible. The residue from uncoated NYCO fabric was a fluffy white solid. These observations clearly demonstrate the efficient Char formation in the case of phosphonium ionic liquid coated samples supporting the observations made during the vertical flame testing.
[221] Amino functionalized phosphonium ionic liquids Tributyl amino propyl phosphonium bromide (TsAP-Br) [222] Amino propyl tributyl phosphonium bromide, here after referred as `TBAP-Be or as 'Fomiula 23'was synthesized by reacting tributyl phosphine with 3-broinopropylarnine hydrobromide. TBAP-Br was tested both by itself and with urea in the FR coating formulation on NYCO fabric.
The combination of TBAP-Br and urea produced excellent results, with an average char length of 4.37 inches, and an average Char yield of 93.1%.
Pure TBAP-Br produced good data as well, with averages of 5.16 inch char length and 91.9% char yield. The vertical flame test data are provided in Table 8. The data indicate that amino functionalized phosphonium ionic liquids are suitable as FR coating materials.
[223] Phosphorus-Nitrogen synergism [224] It is a well-known fact that there exists a phosphorus-nitrogen (P-N) synergistic action. in the flame retardancy of cellulosic fibers. Addition of nitrogen containing compounds, such as urea, cyanamides, dicyandiamide, guanidine salts, and melamine compounds to phosphorus compounds increase their flame retardancy, even -though. the nitrogen containing compounds themselves do not exhibit F.R. property. En TBAP-Br both P and N present in the same molecule. hi this way TBAP-Br is analogous to [TBOP-Br Urea] formulation. The presence of the amino group on TRAP-Br already gives it a potential edge over TBOP-Br because it may not =quire additional nitrogen additives. Without wishing to be bound by theory, it is thought that the mechanism of P-N synergistic action is acting on the FR property of TRAP-Br and TBONBr ionic liquids.
[225] in order to further established the use of hydroxyl or amino functional groups on the ionic liquids, a compound (Tetrabutyl phosphonium bromide) which has chemical structure similar to 'MOP and `1713AP were tested to evaluate how critical is presence of the hydroxyl or amino group in the phosphonium ionic liquid for imparting FR property to the fabric.
The Tetrabutyl phosphonium bromide and Tetrabutyl phosphonium bromide mixed with urea solutions produced average char lengths of 8.2 and 7.1 inches respectively. These values are quite high relative to results of TBAP-Br and [TBOP-.Br]+13rea vertical flame test results, and three of the six samples tested did char .completely. Char yield values were 64.6 percent for Tetrabutyl phosphonium bromide and 75.2 percent for Tetrabutyl phosphonium bromide mixed with urea, both significantly lower than the percentages achieved with TBAP-Br which was greater than 90percent. This data establish that presence of hydroxyl or amino functional groups is important for flame retardant performance of the phosphonium ionic liquids.
12261 Reviews of commonly used flame retardants have shown that halogen containing coatings may have environmental or other health risks associated with them. Bromine compounds, in particular, are under a great deal of serutiny,,with risks of bio accumulated, toxic exposure during processing R. Flotrocks, :flame retardant challenges for textiles and fibers:
New chemistry versus innovatory solutions., Polymer A.,gredditOr and Stability, 96,377-392 (20141. TI3AP and 1130P both have a bromide as.
the anion, but it can be replaced by a number of safer alternatives as provided in Figure I, each with a unique contribution to the compound's.
properties. Three common anions were exchanged with the bromide ion on TRAP-Br to demonstrate the possibility of producing bromine-free flame retardant ionic liquids based on TBAP cation.
[2271 Tributyl-propyl amino phosphonium. dibutylphosphate (TBAP-DBP) [2281 Tributyl-propyl amino phosphonium acetate (TB.AP-Aeetate) [229] The vertical flame test data. of acetate anion is coinpared with other anions of TRAP in Figure 21, All the TRAP-based ionic liquids tested exhibited excellent flame retardant properties with the average. Char length <4.5 in. indicating that the major influence, on flame retardant property is due to 'MAP cation., Among. Various -FHAP-based ionic liquids tested, 'LEAP-Acetate exhibited lowest char length of 4,1 in, This could .be attributed to lower molecular weight of acetate anion and rationalized as follows: With the equivalent coating weight increase (- 35%) in all the TRAP ionic liquids, the concentration of TF3A.P cation is maximum in the caw of 113.AP-acetate, Because' the TBAP cation is the major contributor to the flame retardant property, TBAP-Acetate exhibits the best FR
property among the TBAP ionic liquids tested.
[230] Binder Systems [231] The durability of the FR coating is one of the most important aspects of the application. However, while effective binding systems for cotton fabrics are common, the low reactivity of nylon has made imparting a durable FR coating to 'NYCO fabrics a difficult task. Binding agents for fabrics can consist of polymers such as polyurethane, polyvinyl chloride, polyacrylate, or use. nitrogen containing compounds including but not limited to melamine and urea to link coating molecules to the fabric and create a. network that does not wash off easily.
There are two possible methods of adhering the ionic liquid to the fabric. The first is a reaction mechanism thatbonds the ionic liquid molecule to the fabric directly, either by some type of activation or the presence of a catalyst. The second possible route is to react ionic liquid with another compound or set of compounds that.then bonds to the fabric. A polymeric network of FR compound interlaced within a binding material is a common method for imparting a durable coating to fabrics.
[232] Samples were washed thoroughly with cold water by hand, rinsing the fabric completely to ensure that any washable coating was removed. The AATCC outlines the procedure for commercial washing [Standard Laboratory Practice for Home Laundering Fabrics Prior to Flammability Testing to Differentiate Between dnrable and Non-Durable Finishes, AATCC Monograph, MT, (1991)).
[233] Dimethylol dihydroxyethyhmeurea (DMDHEU) and Dimethylol ethyleneurea (DM:EU) are two common finishing agents that can be used as binders. However, they are primarily used with cellulosic fabrics. A
commercial product Knittex0 7636 (primary ingredient DMDHEU) was tested with a TBAP-Br coating of the NYCO fabric, but less than 20% of the coating applied was retained after just one wash.
[234] in order to determine the potential utility of a binding agent, product samples were tested initially with a solution containing only the binder. If a high amount of the binder coating (>85%) was retained after washing, it was then tested with ionic liquid systems. Lubrizol produces a. variety of finishing applications for textiles, and three products from the company were tested: .PrintRitee 595, an acrylic binder, Vycare 580X182, a PVC
dispersion, and Sancure0 20025F, a polyurethane mixture. Two other acrylic binders from Huntsman Chemical were also tested: Dierylane AC-01 and Dicrylane TA-GP. Finally, a binding system composed of a melamine-fonnaldehyde finishing agent and a urea based cross linker from Emerald Performance Materials were tested. The components are Aerotext) resins, entitled M3, 3730, and 3030.

[235] Varying the amount of the binder often resulted in different retention values, most likely due to compounds' ability to interact with the fabric in the presence of water. [ía given composition of binder was not. durable, alternate compositions were tested until a successful composition was found or the material was deemed unusable as a binding agent.
[236] The acrylic binders (PrintftitelDierylans) provided some retention of the coating, with PrintRite adhering best to the fabric. However, the lack of nitrogen in the compound makes it difficult to impart complete FR
properties to the fabric. Sancure showed very high retention by itself, but formed a separate phase when placed into solution with '['BAP-Br. Its inability to mix in water with TBAP compounds made it unusable for further tests. Polyurethanes react well with hydroxyl groups, which are abundant on the NYC() fabric. The best binding system tbr amine and hydroxyl funtionalized phosphoinium -based ionic liquids determined to be melamine based binder products including but not limited to Aerotex M3 resins available from Lubrizol along with cross linkers including hut not limited to acrylates, aerotex 3030 and aerotex -3730.
[2371 Antieleetrostatie Property [238] In general, textile fabrics are electric insulators with surface resistance in the range of 1013 a to 106 a [P.J. Zilinskas, T. Lozovski, V.
Jankauskas, J. Jurksus, Electrostatic Properties and Characterization of Textile Materials Affected by ion Flux, MATERIALS SCIENCE
(MEDZIAGOTYRA) 19, 201 (2013)1. Surfaces with high electrical resistance are:susceptible for electrostatic charging. An accumulated decide. charge has the ability to generate and retain an electrostatic field of significant magnitude. This electric field can be detected afie a surthce voltage that can be measured. Thus the surface voltage can be a measure of the electrostatic properties of the test fabric (239.1 Ionic liquids consist of charged species with high ionic conductivity, The static charge accumulated on the fabric surface can be rapidly dissipated by conducting ionsõAntistatie property of the T130['-Br/Urea treated fabrics were tested using the Federal Test Method Standard 191A
Method 5931 'Determination of electrostatic decay of fabrics' According to this method the amount of time it takes for static to dissipate from a fabric strip was measured, The 3" x 5" test samples were preconditioned at 20% relative humidity at 24 C. 5000 V was applied to the test fabric An a period of 20 seconds. The. voltage behavior of the Lea sample as a function of decay time was recorded. The time for the charge to decay from the maximum voltage level to 50% of the maximum voltage attained was measured from the voltage decay plot. The decay time for the uncoated and TROP/Urea coated fabrics were provided in Table 6. The electric charge applied on to the THOPArrea coated fabric was rapidly removed compared to uncoated NYC() fabric.
[240] It will be. readily understood by the skilled artisan, that numerous alterations may be made to the examples and instructions given herein.
These and other objects and features of present invention will be made apparent from the. following examples. The following examples as described are not intended to be construed as limiting the scope of the present invention.
EXAMPLES
Example [241] Synthesis of [llydroxy propyl methyl]-imidazolium bromide, [0:14pmim]Br [242] Methyl imidwz.ole (0.063 inol, 5 mi.) was mixed with 3-bromopropanol (0.095 mol, I3.2g) in a round bottom (1W) flask. The mixture was heated to 80 degreeC with a reflux condenser. The reaction continued for 24h.
After the reaction, the top layer was decanted off. The product was washed with diethyl ether (5 mL 3X) and dried under vacuum at 80 degreeC for 2 days and analyzed with proton nuclear magnetic resonance spectroscopy (NMR). Proton NMR Data: 8.866 (s, I H. aromatic). 7.609 (s, Ill, aromatic), 7.547 (s,II1, aromatic), 4.377 (t, 211), 3.976 (s, 311-Ring C113), 3.675 (t, 2E1, -N-C112), 3.592 0,21-1, -012-01.-1), 2.172 (m, 211) Example 2 [243] Synthesis f hydroxybutyl methyl imidazolium chloride [244] 15 mi. of 4-cholorobutanol (.5 mol) was mixed with 7.98 m.L of 1-methyl imidazole and stirred at 80 degC with reflux condenser. The reaction was continued for 24h then cooled to room temperature. The excess tmreacted 4-cholorbutanol was removed by washing with diethyl ether (5 mi., 3X). Then the sample was dried at. 80QC under reduced pressure. Proton NMR Data: 8.856 (s, 111, aromatic), 7.606 (s,11-1, aromatic), 7.583 (s,1 H, aromatic), 4.364 (1, 2E1), 4.364 (211 ---C112-0H), 4,032 (s, 311-Ring CH3), 3.703 (t, 211, -N-C112), 2.034 (t,21I, -CH2-011), 1.676 (m, 211). Corresponding compounds with ethyl imidazole also prepared with 3- bromopropanol and.4-chlorobutanol.
Example 3 [245] Synthesis of [Amino propyl methyl]-imidazolium bromide rapmimp3r [246] 102 g of 3-bromopropylamine hydrobromide (0.456 mol) was dissolved in dry ethanol To this solution 1-methylimidazole (36.4 mlõ 0.456 mol) was added. The mixture was stirred for 24h at 80 deg-C. White solid was tbrmed was recrystallized from ethanol. Proton NMR Data: 8.842 (s, 111, aromatic), 7.580 aromatic), 7.505 (s,11-1, aromatic), 4.378 (t, 211), 3.932 (s, 3H.Ring CR3), 3.103 (t, 211, -N-C112), 2.320 (t,211, -0-12-014), 2074. (t, 2H) Example 4 [247] Ion-exchange with Lithium Bisttrifluoromethylsolfonyl) imide anion [2481 Ionic liquids containing anions other than bromide ion can be prepared by ion-exchaning the bromocompound with alkali salts of other anions. For example, ionic liquids with I3is(trifluoromethyl sulfonyl ) imide anion can be prepared by ion-exchanging the bromide compound with Lithium Bis(trifluoromethyl sulfonyl) imide NITs ub.2), 1 1.28 g of LiNTS ub .2 was dissolved in 50 nit acetone. Then 5 g of ihydrxypropyt-methyl imidazoliumlbromide was added to the Ills (trifluoromethylsulfonyi) imide anion solution and stirred in a 200 int, round bottom flask for 24h. Then 200 inL of deionized water was added to dissolve Lair. Hydrophobic ionic liquid layer settled at the bottom. The solution was decanted to isolate the ionic liquid compound with NIfsub.2 anion. Similarly, amino compound also ion-c...xchanged with LiNTfsub.2 to form the corresponding ionic liquid. Amine- and hydroxyl groups containing ionic liquids when mixed with each other consistently showed higher carbon dioxide absorption capacity compared to the correponding compounds alone, [249] The following examples are focused on preparing new ionic liquids in which both amino and alcohol groups will be present in the same molecule.
Interestingly recent research reports showed that mixing super bases with alcohol containing ionic liquids were found to be effective for equimolar carbon dioxide capture under ambient pressures [C. Wang, H. Lao, X. Lao, H. Li, and S. Dai, Equimolar CO2 capture by imidazolium-based ionic liquids and superbase systems, Green Chem. 12,2019-2023 (2010)1.
However, this systems seems to have low recyclability.
Example 5 [250] Synthesis of ionic liquid represented by the formula 8 Br-"N 41,1--tf;w1; = = utf 114 *1 Br' 4* ar' \ OH
=H
Formula 8 [2511 In a typical reaction, 3 g of aminopropyl-methyl imidazolium bromide was dissolved, in ethanol. 6.9g potassium carbonate and 4.14g of bromopropyl alcohol were added. to this solution and reacted at 50 degreeC
for 12h. Alter the reaction the solvent was removed by rotoevaporation.
The solid was extracted with ether to remove .unreacted bmmopropyl alcohol. The proton mut of the product is provided in Figure 3. The proton nmr distinctly different from the starting material showing that the reaction has proceeded to completion. However, proton correspond to C-2 in the imidazolium ring was not observed in the nmr spectrum. This reaction was repeated several times with various conditions including different solvent, temperatures, and molar ratio of the reactants. In all the variations that we tried the resulting; product was similar and did not show C-2 hydrogen.
Since, the expected product was not obtained, we tried an alternative approach to synthesize amino-alcohol groups containing imidazolium compounds.
Example 6 [252] Synthesis of ibroinopropyl-methyllinddazolium bromide [253] In the alternative method bromoalkyl imidazolium compound was first synthesized. Then this intermediate compound was reacted with various alkanol amine compounds to form the corresponding ionic liquids as bromide salts. 'Die reaction scheme for the synthesis of brornopropyl-methyl imidazolium bromide is provided below:
CH-4 Br-!
>--N
/i 6r Formula 9 E2541 In a typical reaction, 28.5 g (0.134 mol) of 1-methyl imidazole was taken with 55 g (0.201 mol) of I,3-dibromopropane (1:1.5 ratio) in acetonitrile solvent. The mixture was heated to 50 degC. In 3-5 min of addition of methyl imidazole to dibromopmpane, a cloudy solution was formed. The internal temperature was raised to 70 dege during the -further addition of imidazole. The addition of methyl imidazole in acetronihile was controlled such that the reaction mixture temperature remains constant around 55 degC. After completion of the addition of methyl imidazole the reaction mixture was cooled to room temperature. The reaction mixture was rotoevaporated to remove the solvent. Then the white solid formed was washed withdiethyl ether to remove the excess dibromopropane. The dried product contained both monomer and dimers. The required monomer product compound 4 was separated by dissolving in acetonitrile. The proton nmr of the monomer compound bromopropyl methyl imidazolium bromide is provided in Figure 7. The reaction was conducted at various temperatures between 40 to 55 degree C. The monomer yield in the final product was increased with increase in temperature. Further, diluting the reactants in acetonitrile also helped in increasing the monomer yield.
Proton .NMR Data in 1)20: chemical shift 8.82 (s, 1E1), 7.55 (d,11-1), 7.47 (d, 11-1), 4.41 (t, 211), 3.92 (s, 311), 3.47 (t, 211), 2.44 (211).
Example 7 [2551 Reaction of bromopropyl-methyl-imidazolium bromide with aikanol amines [256] Bromoallityl methyl imidazolium bromide can be reacted with a variety of aminoalkanal compounds forming the corresponding ionic liquid. For example, ionic liquid represented by the Formula 10 was synthesized by reacting bromopropyl methyl imidazolium bromide (Formula 9) with N-methyl ethanolamine in the presence of potassium carbonate is provided below.
at-gr= =
'set KZ:(4) H ..
sNatrj µ,04 Formula ID
[257] in a typical reaction, 6 g (0.02 mol) of bromopropyl-methyl imidazole, 1.58g [258] (0.02 mol) of N-methyl ethanolamine and 5.83 g of potassium carbonate 0.04mol) were mixed in 30 mi.: of acetonitrile and heated at 65 degC for lb. After the reaction the solid was filtered off and washed with acetonitrile. The filtrate was rotoevaporated to remove the solvent. Then extracted with tetrahydrofuran (THE) in which N-methyl amino ethanol is soluble. Then the sample is dried under high vacuum. The proton NMR
spectrum of the dried product is provided in Figure 5.
[259] NMR Data: proton NMR in D20 Chemical shift 7.52 (d, 1I1), 7.47 (d, 1H), 4.23 (t, 2H), 3.89 (s, 3}1), 3.69 (t, 2H), 2.58 (t, 2H), 2.51 (t, 21I), 2.25(s, 311), 2.08 (m, 211). This structure was further- supported by C-13 NMR spectrum of the ionic liquid represented by the Formula 10 provided in Figure 6. C43 NMR Data: 122.7 (G), 121.3 (CH), 57.5 (C113), 56.8 (C112), 52.5 (0-12), 46.7 (CII2) 40.2 (013), 34.5 (CH3), 25.2 (CEI2) Example 8 [260] Synthesis of bromopropyl dimethyl-imidazolium bromide was achieved according to the reaction scheme below:
e Br l\IC1-13 Br õNITN-Sr .s-St HC

CH
s 3 Formula U.
[261] To a solution of 1,3-dibromopropane (126.02 g, 0.6242 mol) in 150 mL
of acetonitrile a solution of 1,2 dimethyl imidazole (30 g, 0.3121 mob was added drop wise at 80 degree C. The addition was completed in about 2h.
Then the reaction mixture was left to stir at 75 degree C overnight. After completion of the reaction, the solvent was removed by rotoevaporation under reduced pressure. White dry solid formed was treated with diethyl ether in small batches. Ether extraction was carried out for 3 times. Then the powder was dried to remove ether. Then the dried powder was stirred with acetonitrile at room temperature to isolate monomer bromopropyl compound. The undissolved dimer was separated by filtration. The filtrate was rotoevaporated to remove the solvent and dried under high vacuum.
Yield 20g. The proton NMR of the showed highly pure monomer compound. NM R Data: Proton NMR in 11)20 Chemical shift 7.41 (d, 111), 7.35 (d, 4.31 0, 211), 3.78 (..s, 3171),, 148 (t, 2W. 2.63 (59 3II), 238 (m, 211).
Example 9 [2621 3-i3romopropyl- ,2 dimethyl imidazoliurn bromide compound was reacted with a number of alkanol amines, alkyl amines, cyclic amines, aliphatic cyclic amino alcohols and. compounds such as 2-amino-2-inethy1-1,3 Isropaned io 2-piperidineethanol, 2-piperid 1emethano1, diisopropanol amine, 3-quinucliklinol, N,N-dimethylethanolamine, and 3-piperidino4,2-propandiol and sterically hindered amines to form a variety of ionic liquids containing both alcohol groups and ammo groups. IN-methyl ethanolamine, monoethanol amine and diethanohimine derivatives of the compound represented by the chemical Formula .11 were synthesized high yield in the presence of potassium carbonate. A typical reaction scheme of Formula 11 with N -methyl ethanol amine is provided below.
Br H c-N 9H3 3 y __________________________________ H3C-N ,N+
> \f-Br Formula 12 [263] The proton and C-13 .NNIR. spectra of the ionic liquid represented by the chemical Formula 12 arc provided in Figures .8 and 9, respectively, .(;3 [264] Proton .NlvIR Data: Proton NMR in 1)20 chemical shift 7.35 (d, 11I), 730 (d, 111), 4.12 (t, 2I1), 3.74 (s, 3.11), 3.67 (1, 211), 2.57 (s, 311), 2.48 (m, 211), 2.25 (2, 311), 1.99 (m, 211). C-13 NMR Data:.143.4 (C), 121.5 (CH), 119.9 (CH), 57.8 (012), 57.1 (C112), 52.6 (C112), 45.5 (CH), 40.9(C113), 34.3(C113), 25.4(012), 8.8 (013) Example 10 [265] Reaction of 3-Bromopropy1-1,2 dimethyl imidazolium bromide reacted with =methanol amine molted in the corresponding ethanol amine compound in the presence of potassium carbonate according to the reaction scheme represented below:
Kxo, Br- H
H2N OH ----). Hp-N
0.13 Y" =-=""N"
Formula la [266] Proton NMR. spectrum of the ionic liquid represented by the Formula 13 is provided in Figure 10.
[267] The reaction progress was demonstrated by the shift in the NM R
resonance peaks for C112-13r at 3.477 ppm shifted to C112-N at 3.678 ppm.
This clearly demonstrated the alkylation of amino groups with the bromopropyl-1,2 dimethyl imidazole.

Example 11 [268] The compounds containing both amino and alcohol groups were ion-exchanged with Iiis(trifluoromethylsulfonyl) imide anion to form the corresponding ionic liquids shown in Figure 2. Proton N MR of the Bis(trifluoromethylsulfonyl) imide anion exchanged amino alcohol funtionalized imidzzolium iOniC liquids are provided in Figures 11 to Figure 14. Similarly by ion exchanging with Nal3Fstib.4 resulted in corresponding iOnie hquidS, Offier anions listed in the Figure I can also be exchanged similar to Bis(trifluoromethyl sulfonyl) imide anion and BUsub.4 anion to form the corresponding ionic liquids.
Example 12 12691 Thermal stability of amino alcohol in etional ized ionic liquids [2701 In order to determine the thermal stability of the ftinetionalized ionic liquids synthesized thermogravirnotrie analysis (TGA) was conducted, The decomposition temperature of ionic liquids will provide data on the thermal stability of ionic liquids. The TGA was run on a TA Instruments TGA2950 (TA Instruments P/N 952250.502 SiNIIIA2950-R5 16) at Edison Analytical Laboratofies, Inc., Latham, NY. The purge atmosphere was nitrogen at 100 ml/min. The temperature program was a ramp at 10 degree C per minute to 600 degree C. The sample was in a platinum pan. Data collection used Thermal Advantage software v.1.1A õSiN C1102272 and the analysis used Universal Analysis v. 3.4C build 14Ø10. The instrument was calibrated for temperature using the curie points of nickel and iron and calibrated for weight with the precision weight set provided by TA
Instruments. The ionic liquid represented by the Formula 17 exhibited a larger amount ()floss near 280 degree C compared to the ionic liquid represented by the Formula 14. This can be attributed to the loss of N-methyl group. C.)therwise, the two materials show similar decomposition profiles and both are completely reduced to a black char by 488 degree C.
[271] The ionic liquids reported here show relatively lower stability than the imfunctionalized Its reported in the literature [Z. Zhangõ and R.G. Reddy.
'I:hernial Stability of ionic Liquids, `17MS Annual Meeting held on February 17---21, 2002 http://Www.bama.ua.edui¨zhang002/ research' slideshow6,pdfl. The amino alcohol functionalized ionic liquids are stable up to 280 degree C which is sufficiently high enough for carbon dioxide capture from flue gases and other applications. Further, it is interesting to note that the amino alcohol groups are stable up to 280 degree C. which is not possible to achieve by the physical mixing of amino alcohols or amines with an unfunctionalized ionic liquids or other solvents [D.
Camper, J. tiara, DI,. Gin, R. Noble, Room-temperature ionic liquid-amine solutions: Tunable solvents fur efficient and reversible capture of an, hid.

Eng. (Them, Res. 47, 84964498 (2008)). The TGA of functional ized ionic liquid represented by the chemical Formula 17 under flowing air (20%
oxygen) and nitrogen and air are provided in Figure 15. Both the curves almost overlap indicating that MNII's ionic liquids are stable in nitrogen as well as in air up to 280 degree C.
Example 13 [272] Carbon dioxide absorption by funetionalized ionic liquids 12731 The ionic liquid samples (about 3 g) were loaded in the isochorie cell and degassed at 80 degree C and 3 mbar vacuum for a period of 1248 h.
After cooling the sample to 25 degree C., carbon dioxide gas was introduced into the isoehorie cell. The pressure was set at desired pressure between 1-8 bar, The sample was stirred during the absorption experiment.
The Weight increase due to carbon dioxide absorption was ineasuxed at various exposure times. The absorption duration was kept at 18h for all the samples uniformly. In Figure 16, carbon dioxide absorption of fimctionalized ionic liquids and unfuntionalized ionic liquid hexyl methyl imi daz odium uoromet bylsul fon yl) Imide (C6ituitnNI.12) are compared. Anions strongly organize around the ammo groups forming strong hydrogen bonds. So: it may be possible to achieve high reactivity by using a different anion. Replacing H with CH3 group liberates amino group from the clutches of hydrogen bonding and helps in increasing the reactivity and absorption of carbon dioxide. Further, the amount of carbon dioxide Absorption is drastically increased by the introduction of hydroxyl groups in the proximity of the amino group. The carbon dioxide absorption of C6mimNIT2 unfunctionalized ionic liquid is Kobably attributed to physical mechanisms, while chemical and. physical mechanisms are involved in the carbon dioxide absorption of the amino alcohol functionalized ionic liquids. There are two stages of absorption observed for functionalized ionic liquids. There exists a plateau above 2 bar and below 6 bar pressure indicating the presence of these two mechanisms in the functionalized ionic liquids. Enhanced carbon dioxide absorption observed for functionalized ionic liquids at pressures below 2 bar indicates that the chemical reaction mechanism is acting in the carbon dioxide absorption. The viscosity of the ionic liquids increased with increase in the protons NH2 greater than NH greater than N-CH3. Use of N.C2:115 or NI-C3147 or N-C4H9 or N-aliphatic ring will help in further reducing the viscosity without compromising on the carbon dioxide absorption.
Example 14 [274] Viscosity of Functionalized Ionic Liquids are provided in the Table 1.
Compound I Viscosity .......... isn I Pristine Sample Mier Carbon dioxide absorption Formula 14 1 1608 2510 l'offnula 15684 766 Formula 16 ¨ 4435 4565 Formula 17 407 952 Methyl amino 10,408 propyl imidazolium NIf2 Butyl amino 43%
ProPY1 imidazolium NT11 Methyl hydroxy 179 propyl imidazolium Butyl hydroxy 158 propyl imidzolium Itiexadecyl methyl 69 imidazolium NIT2 Example 15 12751 Flame retardant (FR.) application of containing amino and alcohol group functionalized imidazolium ionic liquids were tested by coating them onto cotton fabrics. For example, 3-hydroxypropy1-1-methyl imidazolium]
bromide [01-1pmim]Br which was prepared using the method described in the Example 1 was coated on to cotton fabric. The flame retardant property of the coated fabric was evaluated using vertical flame testing. The tire is immediately extinguished when the flame was removed while the uncoated fabric turned into ashes in 20 seconds.

[276] Example 16, 17 and I 8 are comparative examples supporting this disclosure that the amino and alcohol groups are critical for the superior FR, property of the ionic liquids.
Example 16 [277] 1-But-3-eny1-3-methyl-1.11-imidazolium bromide B
1-iõC
-N
Formula 18 [278] Methyl imidazole (2.06 g) was mixed with 4-bromobut-1-ene. (4g) in a round bottom (RB) flask. The mixture was stirred at 40 C for overnight.
After the reaction, the product was washed with diethyl ether (5 ml 3X) and dried under high vacuum. 1-810-3-enyl-3-methyl-lii-imidazolium bromide was obtained as a clear viscous yellow colored liquid. The dried sample was analyzed with proton nuclear magnetic resonance spectroscopy (NMR). Proton NMR. Data: (DMSO-D6): chemical shift [ppm] 2.72 (211, 2'41), 4.11 (s, 311, NOB), 4.48 (t, 214, l'-H), 5.09-5.11 (in, 111, 5.81 (m, 111, 3'-H),7.62 (s, 111, 441,4-11/5-H), 7.65(s, 111õ 4-11, 4-11/5-H),

10.19 (s, I H. 2-H).
Example 17 [279] imidazolium bromide Br Formula 19 [2801 in a typical reaction, 20 g of ally1 bromide was added in drop wise to 13.4 g of methyl imidaz.ote in a RB flask. The temperature of the reaction mixture was kept below 10 degree C using an ice bath. After the completior of addition of allyl bromide the mixture was stirred at room temperature for 12 'hours. The final product was obtained as a reddish brown liquid after washing with diethyl ether and the volatiles were removed by high vacuum evaporation at room temperature, Proton NMR
Data: (DM SO-D6): chemical shill ¨ 9.27 (s. IH. NCHN), 7.78 (S, 2H, NCHCHN), 6.05 ( in, I H. NCH2CH4C112). 5.32 (dd. III, NCI-UCH@
Clilltrans), 5.29 (dd. I H. NCH2CIFICHeis), 4.90 (d. 5.8 Hz, al, NCH2C11@ C112), 3.84 (s, 311, NCH3.) Example 18 [281] Vertical Flame Testing [282] 50 Nylon 50 Cotton Universal riustop fabric class 6 MIL-MT-4443613 pure finish (NYCO) fabric samples were coated with aqueous solutions of 1-But-3-enyt-3-methy1-1H-imidazoli um bromide and 1-ally1-3-methyl imidazolium bromide and cured at 70 degree C for 10 minutes. Vertical .flame testing data for ionic liquids based on methyl imidazolium bromide containing Carbon-Carbon double bonds are provided in lable 2. None of these ionic liquids with terminal double bond performed well under vertical flame testing.. The after flame times were very high with low char yield (less than 20 percent) as provided in Table 2.
12831 Table 2. Vertical flame testing data of ally' and butenyl methyl-imidazolium bromide ionic liquids Coating Avg. Avg. Avg. Char Composition in Weight Char After Yield water increase Length Flame of fabric (in). Time (s) 50% Allyi-methyl- 13.5%
34.6% 43.5 imidazolium 20% I-Ally1-3- 5.9%
.imadazolium/30%
AMPS/5% 45.8% NA 42.5 MBAmil% AN
50% Allyl-methyl- I 9.9%
imidazolium/12.5% 40.7% NIA 43 Urea Example .19 [284] This is a comparative example. Flame resistance of two ionic liquids tetrabutyl phosphonium diethyl phosphate (TPEP) and Ethyl methyl imidazolium diethyl phosphate (OP) coated 419W cotton fabrics were measured. according to standard test method ASTM 6413-08. The specimens with dimensions 3" x 12" were used in this test. The specimen was maintained in a static, draft-free, vertical position. The test specimen was exposed to a flame height of 1-1/2 inch (38 mm) for 12 seconds. After the 12-second period, the after-flame and atler-glow times were determined. The char length was measured after cooling the sample. The ionic liquid coated fabrics were charred and stopped the flame propagation immediately after the removal of the flame. Vertical flame testing of TPEP
and EIP based FR fbnnulations are provided in Table 3.
[285] Table 3. Vertical flame testing of commercial ionic liquids TPEP
and Fit' Coating Solution Fabric Avg. Avg. Avg.
type Weight After Char Increase Flame Yield Time (s) TPEP/13 .6% A 1 (NO3)3 1) Cotton 29,7% 4.3 26.7 0% TPEP/10% EIP (2) Cotton 28.1% 1.5 41.4 0% TPEP (3) 'Cotton 22.5% 6 10.5 25 % 13.113 (4) Cotton 28.3% 3,5 15.5 25% IRFT/6.7% Urea NYC() 24.3%
:38.7 41.1 (NYCO) Example. 20 [2861 The ionic liquid (PEP and HP) coated fabrics formed char during flame testing. But they also exhibited higher char length. In order to improve the flame retardant property, the IPEP-coated cotton fabric was coated with a layer of AMPS (30%) monomer and MIlAm (3%) cross linker. Then the fabric was air dried fir 4 days before the vertical flame testing. Cotton fabric, coated with IPEP/AMPS-MBAtn was subjected to vertical flame testing. The coated fabric exhibited a less vigorous flame than the uncoated control fabric. At time and char length was also significantly reduced and no afterglow was observed. The vertical flame test data were provided in Table 20.
[2871 Table 4. Vertical flame testing of AMPS coated cotton fabrics Coating Solution Avg. Avg. Char Avg.
Char Weight Length Yield ()A) increase (in) 20% AMPS/3% NIB Amil ')/;.) 15.8% 18%
APS
20% AMPS/6% :MBAm11% 18.4% 9.3 63.9%
APS
20% AMPS/9% MBAmil% 20.6% 10.1 57.6%
APS
3010 ANIPS/3% MBA mil% 25.1% 9.1 67.6%
APS
30% AMP S/6% MBAm/1% 26.6% 5.9 90.5%
APS
30?:'.O M11 /9 MB A in/ 1 30% 7.1 83.9%
APS
Example 21 [288] Table 5. Vertical flame testing of AM PSrl`PEP coated cotton fabrics Coating Solution. Avg. Avg. Char Avg.
Weight Length Char Increase (cm) Yield 20% AMPS/4% MBAm120% 43.3% 24 87.7%
TPEP/1.% APS
Alternating layers: 20% TNT 48.6% 23.4 88.1%
and 30% AMPS/6%
MBAm/1% APS, 2 layers each _____ Alternating layers: 20% TPEP 51.4% 24.5 82.2%
and 20% AMPS/4%
MBAmil% APS, 2 layers each Alternating layers: 45% 'PEP 47% 20.9 85.5%
and 30% AMPS/6%
MBAmil% APSõ 2 layers each Example 22 [289.] Synthesis of Tributyl hydroxyl propyl phosphonium bromide (MOP) 12901 Hydroxy propyl tributyl phosphonium bromide, [Bu3PrIPITI)Pfir also referred as 41130P-Be or 4.Formula 22" in this disclosure was synthesized by reacting tributyl phosphine, [Bu3P] with brow propanol. 1-Bromo propanol and tributyl phosphine was mixed in. a round-bottomed flask at 60 -100 "C with constant stirring tbr 1.2-24h. The reaction product was washed with diethyl ether and completely dried under vacuum at 80 degree C.

[291] ChemicA structure of "TB(W-Br" Formula 20 Bi P OH
CH3 FOrtntaa 20 Example 23 [2921 llydrokypropylphosphoniUM bromide (Formula 20) prep red usin,g the method described in the example 22 was dissolved in hydrogen bromide and heated under reflux for five hours to obtain the bromopropyl phosphonium salt represented by the chemical of the .10rinula. 21.
Br-.
H3C, 013 Formula 21 Example 24 [2931 gromopropyl tributyl phosphonium salt (Formula 21) was reacted with a variety of amino alcohols to form the corresponding bromide salts. For example, Bromopropyl tributyl phosphonium bromide was reacted with N-methyl ethanolamine in the presence of potassium carbonate as provided in the reaction scheme below:
K CO2, Formula 22 [294] In a typical reaction, 0.02 mol of bromopropyl tributyl phosphonium bromide, 0.02 mol of N-methyl etlitmolamine and 0.04 mot of potassium carbonate were mixed in 100 mL of acetonitrile and heated at 65 degree C
for 12 hours. After the reaction the product was filtered off and washed with acetonitrile. The filtrate was rotoevaporated to remove the solvent.
Then extracted with tetrahydrofuran Min in which N-methyl amino ethanol is soluble. Then the sample is dried under high vacuum.
Example 25 [295] Termogravimetric analysis of Formula 20 (TROP-Br) coated NYC() fabric [296] Thermogravimetric analysis (TGA) can be helpful in deducing the decomposition mechanism of flame retardant coated fabric. Therefore, the thermal degradation behaviors of uncoated NYC() (control) and TI30P-Br/Urea coated NYC() fabrics were analyzed using TGA. TGA curves were obtained using a TA Instruments T0A2950. The purge atmosphere was air at 100 ml/min. The temperature program was a ramp at 20 degree C
per minute to 600 degree C with a 15 minute hold. The sample was in a disposable aluminum liner in a platinum pan for weight with the precision weight set provided by TA Instruments. High thermal stability of TBOP-Br ionic liquid was clearly demonstrated by the TGA curve provided in Figure 17. The initial decomposition temperature of TBOP is about 290 degree C.
Thermal decomposition of NYCO fabric in air occurs in two stages according to the TGA data provided in Figure 17. The first stage decomposing temperature of uncoated-NYCO fabric is 342 degree C
corresponds to the decomposition of cotton in the NYC() fabric. This decomposition temperature is shifted to 311 degree C by the phosphoni um catalyzed decomposition of cotton. This behavior is similar to the behavior of Tetrakis(hydroxymethyl) phosphonium chloride (UPC) flame retardant material. But the initial decomposition temperature of Till)C is around 184 degree C compared to 311 degreeC for TBOP-Br indicating the relatively higher thermal stability of TBOP-Br. The second stage weight loss is centered around 446 degreeC is due to the decomposition of Nylon material in the NYCO fabric. This decomposition temperature is also decreased in the TBOKUrea. coated NYC() fabric. The residue from sample11301?-Br/Urea coated fabric was a rigid black solid with the original sample form and fabric weave patterns visible. The residue from uncoated NYCO fabric was a fluffy white solid. These observations clearly demonstrated the efficient Char formation in the case of phosphonium ionic liquid coated samples supporting the observations made dtuing the vertical flame testing.
Example 26 12971 Antielectrostafic Property of ionic liquids [298] ionic liquids consist of charged species with high ionic conductivity.
The static charge accumulated on the fabric surface can be rapidly dissipated by conducting ions. Antistatic property of the TBOP-BriUrea treated fabrics were tested using the Federal Test Method Standard 191A.
Method 5931 'Determination of electrostatic decay of fabrics'. According to this method the amount of time it. takes for static to dissipate from a fabric strip was measured. The 3" x 5" test samples were pre-conditioned at 20% relative humidity at. 24 C. 5000 V was applied to the test fabric for a period of 20 seconds. The voltage behavior of the test sample as a function of decay time was recorded. The time for the charge to decay from the maximum voltage level to 50% of the maximum voltage attained was measured from the voltage decay plot. The decay time for the uncoated and TBOP/Urea coated fabrics were provided in Table 6.

[2991 Table 6. Antistatic property of TBOP-BriUrea coated NYCO
samples SampleType Electrical Charge Decay Time (s) Uncoated NYCO .1110P coated NYCO
Warp 7.8 1,2 Fill 9.0 I.) [3001 The antistatic property of the ionic liquid coated fabric was clearly demonstrated in the data provided in the Table 6. The electric charge applied on to the TBOP-BrtUrea coated fabric was rapidly removed compared to uncoated NYCO fabric.
Example 27 [301] Table 7. Vertical flame testing data of THOP-Br ionic liquid Coating Composition Ava Avg. Avg.
on NYCO fabric Weight Char After Flame Increase Length Time (inch) (seconds) 50% T130P-Br 35 - 36.3 50(!io' TBOP-13r/4.5%
38.2% 4.3 2.5 Urea Example 28 [302] Formula 23 - Tributyl amino propyl phosphonium bromide (TBAP-Br) 13031 Amino propyl tributyl phosphonium bromide, [Bu3Pr[Nfl2)]PHr also referred as *TBAP-Br' or 'Formula 23" was synthesized by reacting tributyl phosphine, [13u311 with 3-bromopropylamine hydrobromide. 3-bromopropylamine hydrobromidt: and 1-methyl imidazole was mixed with acetonitrile in a round-bottomed flask at SO C with constant stirring for 12-24h. The reaction product was washed with hexane to remove unre.aeted reactants and completely dried under vacuum at 80 degree C.
*ie.) I
Br 'Ise Br m/ =
Formula 23 1304] Proton NMR (CDC13) Data: chemical shift 0.93 (t, 911; CI13), 1.47-1.63 (in, 1211; C1-1-2), 2.25-2.39 (M, 811; P0-12), 2.9 (in, 211, CH2N112), 3.3$ ppm (t, 211, CII2N1-12); P-31 .NIMIR DATA: chemical shift 34 ppm corresponding to phosphoni um salt Example 29 [3051 Vertical _Flame Testing of TRAP431-[306] TRAP-Br was coated onto NYC() fabric with and without mixing with urea. The combination of TRAP-Br and urea produced excellent results, with an average char length of 4.37 inches, and an average char yield of 93.1%. Pure `rBAP-Br produced good data as well, with averages, of 5.16 inch char length and 91,9% char yield, The vertical flame test data are provided in Table 8. Phosphorus-Nitrogen synergism [307.1 It is a well-known fact that there exists a phosphorus-nitrogen (P-N) synergistic action in the flame retardancy of cellulosic fibers. Addition of nitrogen containing compounds, such as area, cyanamides, dicyandiamide, guanidine salts, and melamine compounds to phosphorus compounds increase their flame retardancy, even though they themselves do not exhibit FR property. In TRAP both P and N present in the same molecule, in this way TRAP is analogous to [TBOP + Urea] fbrmulation.
[308] Table 8. Vertical flame test data of TRAP and TRAP/Urea coated NYCO fabrics Coating Avg. Avg. Char Avg. Char Composition Weight Length (in) After Yield in water Increase Flame Time (s) SO% TRAP-Br 39,3% 5.16 7.0 91.9%
Formula 23 50% TRAP-8r17.0% Urea 38.2% 4.37 2.0 93.1%
on NYCO
Example 30 [309] Bromide low-exchange of TRAP-Br [310] Tribu tyl-propyl amino phosphonium di butyl phosph a te (TBAP-DBP) Formula 24 [311] TRAP with a dibutyl phosphate (DB?) anion was prepared by dissolving equimolar amounts of TRAP-Br and DBP in methanol, followed by the addition of an equimolar amount of potassium hydroxide. The mixture was stirred tbr .12 hours and the resulting in TRAP-DBP ionic liquid and a potassium bromide salt. The methanolie solution was filtered and evaporated under vacuum, to separate the TBAP-DBP ionic liquid. The ion-exchange reaction can represented as follows:
+Mt ( 'KV
\
\
'µµµµµ", s';34 CT%
\ ......................................................... 04, TBAP.DBP
Proton NMR and C-13 NMR spectra of TBAP-.DBP ionic liquid were provided in Figure 18 and 19 mspectiriely.

[312] Since TBAP-DBP has two P-moieties, it was necessary to adjust the TRAP-DBP/t5rea ratio in the FR coating to achieve best FR performance.
The TBAP-DBP/Urea molar ratio was varied between 4:1 to 2:5 and the vertical flame test data are provided in Figure 20 and Table 9. Lowest char length (4,1 inch) and best char yield (91.%) were observed with 1:2. TI3AP-DBP/Urea molar ratio. These data clearly demonstrate the action of 'Phosphorus-Nitrogen synergism' on the flame retardant property of phosphonium based chemicals with the optimum P:N ratio of 2:1 [313] Table 1. Vertical Flame Testing Data of TRAP-DEW
Coating Composition in Avg.
Avg. Char Yield water Weight After flame Increase Time (s) 504 TBAP-DBP/1,5'.b tfrea 36.7% 1.0 50% TBAP-DB P/2, 1% Urea 37.33 2.0 85.6%
50% TBAP-DI3P/3.1% Urea 32.3% 2.0 85.0%
50% TBAP-DBP/5.5% Urea 34.7% 7 7.8%
50% TBAP-DBP/9.5% Urea 39.9% 0.7 90.6%
50% TBAP-DBP/ 12.8%
38.0% 1,0 90.6%
Urea 50% TRAP-IMP/I 6% Urea 36.4% 4.7 817%

Example 31 [314] Tributyl-propyl amino phosphoninm acetate (MAP-Acetate) Formula 25 [315 Bromide anion was replaced with the acetate anion (CITA:00) by dissolving equimolar amounts of TBAP-Br and potassium acetate in methanol. The exchange occurred while stirring for 24 hours, and the final -product of TBAP-Acelate was.isolated through 'vacuum drying and washing with acetonitrile. Potassium salts provide an efficient means of bromide ion exchange as the Kik' prodnetis:easily separated from the product by filtration due to its insolubility in .acetonitrile.
[316] The vertical flame test data of acetate anion is compared with other anions of TBAP in Figure 21 All the TBAP-based ionic liquids tested exhibited excellent flame retardant properties with the average char length <4.5 in* indicating that the major influence on flame retardant property is.
due to '111AP cation.
[317] Among various TBAP-based ionic liquids tested, TBAP-Acetate exhibited lowest char length of 4.1 in. This could be attributed to lower molecular weight of acetate anion and rationalized as follows: With the equivalent coating weight increase. WO in all the TBAP ionic liquids, the concentration of MAP cation is maximum in the case Of TBAP-acetate.

Because the MAP cation is the major contributor to the flame retardant property, TBAP-Acetate exhibits the best FR property among the TRAP
ionic liquids tested.
Example 32 [318] The flammability of organic carbonate electrolyte (DMC) and fire quenching action of amino-functionalized phosphonium ionic liquid was demonstrated in Figure 22. When DMC was flashed with a propane gas burner it immediately catches fire and is completely consumed by the flame.
In contrast, MAP-Br as well as TBAP-Br/DMC mixtures when. torched with propane gas burners quenches the fire in less than 10 seconds demonstrating the flame retardant property of the phosphonium based ionic liquids. The flame retardant phosphonium ionic liquids can be applied as electrolytes or electrolyte additives in lithium ion batteries.
[319] Example 33 [320] Melamine-Formaldehyde Condensate resins including but limited to Aerotex. resins M3 were mixed with cross-linkers including but not limited to Aerotex 3730 tested with TBAP/MOP material fbr FR, properties and coating durability. A typical preparation of durable FR Coated NYC() fabric involved, the following steps. FR coating solutions were prepared by mixing 30 g TRAP-Br, 43 grams of Aerotex M3 and 9 grams of Aerotex 3730 in 60 nil, of water. The solution was stirred until clear, and then 0.6g ammonium chloride was added. Fabric samples were placed in cans along with the coating solution and agitated in a launderOmeter for 45 minutes at room temperantre. The wetted samples were then run through a padder at 5 psi and cured at 150'C fOr two minutes in an oven. Two of each set of samples were flame tested unwashed to determine initial FR
performance, and subsequent samples were washed with cold water and then flame tested to evaluate durability of the coating Vertical flame testing data as a function of binder and cross-linker concentration keeping the TRAP-Br concentration constant is provided in Table 10.
[321] Table .10. Vertical flame testing as function of Melamine -Formaldehyde Condensate and crosslinking agent concentration Melamine- Unwashed Washed Char Fommidehyde Crosslinker Char Length Length (in.) Condensate (in.) 7.5 15 7:75 9 8 12 7 8.5 =
8.5 17 5.75 8 8 10,7 7.25 8.5 [322] Other modifications and variationfi:to the invention will he apparent to those skilled in the art from the foregoing disclosure and kadlinS. Thus, while only certain embodiments of the invention have been specifically described herein, it will be apparent that numerous modifications may be made thereto without departing from the spirit and scope of the invention.

Claims

WHAT IS CLAIMED IS

1. An ionic liquid represented by the structure of the following Formula 1:
wherein (a) R1 and R2 are each independently H, or a C1 to C12 straight-chain alkyl group or brandied alkyl group or aryl group, (b) m is an integer 1 to 6, (c) X is -N(R3)-(CH2)q-OH, wherein R3 is H or C1 to C6 straight-chain or branched alkyl group and q is an integer from 2 to 4, and (d) A- is an anion selected from the group consisting of [BF4]-, [PF6]-, [CH3CO2]-, [HSO4]-, [CF3SO]-, [(CF3SO2)2N]-, [(CF3SO2)3C]-, [SO4]2-, Cl-, Br-, I-, [N(CN)2]
-, [(PO4)(C4H9)2]-, [(PO4)(C2H5)2]-, [(PO4)(C6H5)2]-, [CH3CH2OSO3]-, [CH3OCO2]- and amino acid.
2. A fire retardant coating for textile fabrics comprising the ionic liquid of claim 1.
3. A solvent for carbon dioxide capture comprising the ionic liquid of claim 1.
4. An electrolyte in a lithium ion battery comprising the ionic liquid of claim 1.

5. A flame retardant additive to an electrolyte in a lithium ion battery comprising the ionic liquid of claim 1.
6. An electrolyte in a metal air battery comprising the ionic liquid of claim 1.
7. A flame retardant additive to an electrolyte in a metal air battery comprising the ionic liquid of claim 1.
8. An ionic liquid represented by the structure of the following Formula 2.:
wherein (a) R1 and R2 are each independently H. or a C1 to C12 straight-chain alkyl group or brandied alkyl group or aryl group, (b) m is an integer 1 to 6, (c) X is -NR3)-(CH2)q-OH, wherein R3 is H or C1 to C6 straight-chain or branched alkyl group and q is an integer from 2 to 4, and, (d) A- is an anion selected from the group consisting of [BF4]-, [PF6]-, [CH3CO2]-, [HSO4]-, [CF3SO3]-, [(CF3SO2)2N]-,(CFSO2)3C]-,[SO4]2-, Cl-, Br, I -, [N(CN)2]
-,[(PO4)(C4H9)2\-,[(PO4)(C2H5)2]-, [(PO4)(C6H5)2]-, [CH3CH3OSO3]-, [CH3OCO2]- and amino acid.

9. A fire retardant coating for textile fabrics comprising the ionic liquid of claim 8, 10. A solvent for carbon dioxide capture comprising the ionic liquid of claim 8.
11. An electrolyte in a lithium ion battery comprising the ionic liquid of claim 8.
12.. A flame retardant additive to an electrolyte in a lithium ion battery comprising the ionic liquid of claim 8.
13. An electrolyte in a metal air battery comprising the ionic liquid of claim 8.
14. A flame retardant additive to an electrolyte in a metal air battery comprising the ionic liquid of claim 8.
15. A ionic liquid having flame retardant property, the ionic liquid comprising Formula 3:
wherein (a) R1 and R2 are each independently H, or a C1 to C12 straight-chain alkyl group or branched alkyl group or aryl group, (b) in is an integer 1 to 6, (c) Z is -OH or NR3R4, where R3 and R4 are each independently H or C1 to C6 straight-chain or branched alkyl group, and, (d) A- is an anion selected from the group consisting of [BF4]-, [PF6], [CH3CO2]- , [HSO4]-, [CF3SO3]-, [(CF3SO2)2N]-, [(CF3SO2)3C)-, [SO4]2-, Cl-, Br-, I-, [N(CN)2]
-, [(PO4)(C4H9)2]-, [(PO4)(C2H5)2]-, [(PO4)(C6H5)-, [CH3CH2OSO3]-, [CH3OCO2]- and amino acid, and wherein the ionic liquid has flame retardant property 16. A fire retardant coating for textile fill-tries comprising the ionic liquid of claim 15.
18. An electrolyte in a lithium ion battery comprising the ionic liquid of claim 15.
19. A flame retardant additive to an electrolyte in a lithium ion battery comprising the ionic liquid of claim 15.
20. An electrolyte in a metal air battery comprising the ionic liquid of claim 15.
21. A flame retardant additive to an electrolyte in a metal air battery comprising the ionic liquid, of claim 15.
22. A method of preparing the ionic liquid represented by the Formula 1 of claim 1, the method comprising refluxing a compound comprising Formula 4 with an amino alcohol and potassium carbonate in the presence of a solvent, wherein Formula 4 comprises the following structure wherein (a) R1 and R2 are each independently H, or a C1 to C12 straight-chain alkyl group or branched alkyl group or aryl group, (b) m is an integer 1 to 6, (c) H is CI, Br, I, (d) A- is Cl-, Br- I-, and, whereby the ionic liquid of Formula I is obtained.
23. A method of preparing the ionic liquid of the Formula 2 of claim 8, the method comprising refluxing the compound represented by the Formula 5 with an amino alcohol and potassium carbonate in a solvent, wherein Formula 5 is the following structure wherein (a) R1 and R2 are each independently H, or a C1 to C12 straight-chain alkyl group or branched alkyl group or aryl group, (b) m is an integer 1 to 6, (c) H is Cl Br, I, and, (d) A- is Cl-, Br-, I-, whereby Formula 2 is obtained.
24. A flame retardant fabric product comprising a fabric, a flame retardant ionic liquid represented by Formula 3, and a binder.
wherein about 1% to about 60% by weight of the flame retardant fabric product comprises the flame retardant ionic liquid, wherein the fabric is selected from the group consisting of Cotton, Cellulose, Rayon, Nylon, Polyester, Polyurethane Polyamide, and Aramid.
25. A method of preparing the flame retardant fabric of claim 24, the method comprising:
a) coating the fabric with the flame retardant ionic liquid represented by Formula 3 and the binder to obtain a coated fabric, and, b) curing the coated fabric at a temperature of about 20 degree C to about 300 degree C for about 1 minute to about 12 hours.