Patent Grant
10384090
The present invention relates generally to treatments for substrates and, more particularly, to treatments of fabrics and textiles.
Some materials, including, for example, garments, worn by first responders and soldiers are conventionally pretreated to protect the wearer from exposure to poisonous chemicals. The pretreatments can be applied to a wide variety of surfaces and substrates including, for example, coatings, textiles, plastics, metals, ceramics, and polymers. In operation, the treatments usually detoxify poisonous chemicals by oxidation or by preventing skin contact through repellant coatings and absorbents.
However, these conventional treatments often damage or degrade the surface or substrate on which it is applied. Alternatively, or additionally, the conventional treatments cause respiratory irritation and/or contact dermatitis in the wearer. Moreover, the conventional treatments are stoichiometric in nature—that is, each molecule of the conventional treatments neutralizes, decontaminates, or otherwise reacts with a particular number of molecules of the poisonous chemical. In some instances, the stoichiometry is one-to-one. Therefore, and over time, the treatment becomes less effective and may, in other words, wear out or be rendered completely ineffective.
Accordingly, there remains a need for substrate treatment chemicals by which a wide range of poisonous chemical agents can be neutralized so as to protect the wearer, while limiting damaging effects on the substrate or surface on which it is applied. Furthermore there is a need for pretreatment chemicals that are not respiratory irritants and/or dermatological irritants.
The present invention overcomes the foregoing problems and other shortcomings, drawbacks, and challenges of the conventional substrate treatment chemicals. While the invention will be described in connection with certain embodiments, it will be understood that the invention is not limited to these embodiments. To the contrary, this invention includes all alternatives, modifications, and equivalents as may be included within the spirit and scope of the present invention.
According to one embodiment of the present invention, a method of using a select Schiff base compounds for chemical agent detoxification includes applying a compound to the contaminated substrate. The compound includes an imine having at least one Schiff base nitrogen and an alkyl substituent or an aryl substituent having an electron acceptor. The at least one Schiff base nitrogen is spaced away from the electron acceptor by a distance ranging from about 200 pm to about 1000 pm. The substrate and the compound are dried. The at least one Schiff base nitrogen of the compound promotes a nucleophilic attack on an electrophilic site of the toxic chemical agent.
Another embodiment of the present invention is directed to a method of preparing a detoxifying substrate by selecting a compound for detoxifying a toxic chemical agent having at least one leaving group. The compound includes at least one Schiff base nitrogen that is separated from an alkyl substituent or an aryl substituent having an electron acceptor by a distance that ranges from about 200 pm to about 1000 pm. A quantity of the compound is applied to the substrate and, optionally, the substrate is dried.
Still another embodiment of the present invention is directed to a method of pretreating a substrate to resist toxic chemical agent contamination includes applying a compound to the contaminated substrate. The compound includes an imine having at least one Schiff base nitrogen and an alkyl substituent or an aryl substituent having an electron acceptor. The at least one Schiff base nitrogen is spaced away from the electron acceptor by a distance ranging from about 200 pm to about 1000 pm. The substrate with the compound is dried. When the pretreated substrate is exposed to a toxic chemical agent, the at least one Schiff base nitrogen of the compound promotes a nucleophilic attack on an electrophilic site of the toxic chemical agent.
Additional objects, advantages, and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be leaned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present invention and, together with a general description of the invention given above, and the detailed description of the embodiments given below, serve to explain the principles of the present invention.
It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the sequence of operations as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes of various illustrated components, will be determined in part by the particular intended application and use environment. Certain features of the illustrated embodiments have been enlarged or distorted relative to others to facilitate visualization and clear understanding. In particular, thin features may be thickened, for example, for clarity or illustration.
The present invention relates to compounds for chemical agent detoxification and methods of applying the compounds to substrates for detoxification thereof or treatment prior to exposure to the chemical agent.
As used herein, “alkyl” means a branched or unbranched, alkane or alkene substituent consisting of carbon and hydrogen, for example, methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl.
As used herein, “aryl” means a cyclic, aromatic substituent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenylyl.
As used herein, “Schiff base nitrogen” is defined as the nitrogen atom of a carbon-nitrogen double bond, wherein the nitrogen atom is chemically bonded to the alkyl or aryl and not to a hydrogen atom.
As used herein, “substituted” is defined by the substitution of a hydrogen on a carbon by a univalent group including, but not limited to, halogen, hydroxy, thiol, amino, nitro, cyano, C1-C4 alkyl, alkylamino, carboxy, amido, vinyl, and C1-C5 alkoxy.
“Lewis acid,” as used herein, is defined as a chemical substance that can employ an electron lone pair from another molecule.
“Lewis base,” as used herein, is defined as any chemical substance that donates a pair of electrons to a Lewis acid.
“Tautomers,” as used herein, are structural isomers of organic compounds that are in dynamic equilibrium due to the migration of a proton.
Referring now to the figures, and in particular to
If desired, the pretreatment chemical may further comprise a cross-linking agent that is configured to form a cross-linkage chemical bond between the pretreatment chemical and a substrate.
It will be readily appreciated by the skilled artisan that the pretreatment chemical 12 illustrated in
According to another embodiment of the present invention, a pretreatment chemical comprises a catalyst configured to react with Lewis acids, the catalyst having an electron acceptor (for example, an acidic proton) spaced away from a Schiff base nitrogen by a distance that ranges from about 200 pm to about 1000 pm (or from about 2 bond length radii to about 10 bond length radii). More specifically the catalysts are configured to react with and detoxify toxic pesticides and potent nerve agents, including, for example, phosphoric acid esters (sarin, soman, VX, diisopropyl fluorophosphates, etc.), and blister agents, (such as bis(2-chloroethyl) sulfide) having at least one leaving group. Examples of leaving groups may include, but are not limited to, one or more halide ions, thiolates, amines, alcohols, perfluoroalkylsulfonates, tosylates, and cyanide. The remaining electrophile may contain phosphorus, sulfur, arsenic, or nitrogen.
While not wishing to be bound by theory, it is believed that, for example, phosphoric acid esters may be decontaminated with the pretreatment chemicals of the present invention in accordance with the mechanism illustrated in
A similar mechanism, although not shown, is expected for an opthamolic drug, diisopropyl fluorophosphates (a cholinergic molecule), and the nerve agent, soman (0-pinacolyl methylphosphonofluoridate).
Mustard compounds, such as 2-chloroethyl ethyl sulfide and bis(2-chlorethyl)sulfide, are also expected to follow a similar mechanism. That is, a lone pair of electrons from the Schiff base nitrogen serves as the Lewis base and attacks the #2 carbon bonded to the chlorine or the α carbon bonded to sulfur in the episulfonium configuration. In concerted fashion, the chlorine picks up the local acidic hydrogen. In the presence of water, the phenolate ion from 8-HQ regains a proton from a local water molecule, and the remaining hydroxide allows regeneration of the catalyst to form from the water. Such a mechanism results in either elimination to form a vinyl product (anhydrous), or, in the presence of water, substitution to form thiodiglycol or 1,4-oxathiane, all of which are acceptably nontoxic decontamination products.
A similar mechanism is also expected for treatments against toxic industrial chemicals, such as acrolein (CH2CHCHO), that is, through a catalytic reduction to 2-propen-1-ol in the presence of atmospheric water vapor.
Resonance tautomers of 8-HQ and BIT are shown in
With reference now to
With the pretreatment chemical selected, a quantity of the selected pretreatment is applied to a substrate (Block 34). The substrate, while referenced here as being a fabric or textile, may include any suitable coating, textile (woven and nonwovens), plastic, metal, ceramic, polymer, and so forth. Application of the pretreatment chemical may be direct, that is, without dilution, or by dissolving or suspending a quantity of the pretreatment chemical in an organic or aqueous solvent (for example, a 0.1%-30% solution) that is then applied to the substrate. In any event, the pretreatment chemical may bind to (for example, via cross-linking) or otherwise be retained by (for example, via intercalation) a material comprising the substrate. With respect to cross-linking, the pretreatment chemical may include conventional cross-linking chemistries including, for example, siloxanes, acrylates, radical polymerization, epoxides, and so forth. Generally, application of the pretreatment chemical may range from about 0.1 wt. % to about 5.0 wt. %.
If desired or necessary, the substrate may optionally be dried (Block 36). Drying may additionally or alternatively include heating, for example, in an oven (such as with exemplary temperatures ranging from about 75° C. to about 200° C.) or microwave. However, drying at temperatures above about 200° C. may damage textile fibers, melt polyolefins, or both. Cross-linking by drying may include an initiator, which may be a chemical initiator, light, or other forms of electromagnetic radiation. According to some embodiments including siloxanes, cross-linking may also occur with changes in pH.
It will be readily appreciated by those of ordinary skill in the art having the benefit of the disclosure provided herein that a plurality of pretreatment chemicals according to various embodiments of the present invention may be applied to the same substrate. In that regard, applications of pretreatment chemicals may be simultaneous or sequential. As shown in
It would also be appreciated that the pretreatment chemical may be applied to substrate prior to or after manipulation of the substrate. For example, fabric comprising a garment may be treated prior to or after garment construction. Therefore, the treated substrate may optionally be used to construct a product, for example, a garment or headgear, or activated carbon, carbon beads, or carbon cloth (Block 40). Otherwise, although not specifically shown in
According to still other embodiments of the present invention, the substrate may be treated after exposure to an agent. In that regard, the treatment may be for purposes of remediation, demilitarization, or detoxification rather than protection or prevention.
The following examples illustrate particular properties and advantages of some of the embodiments of the present invention. Furthermore, these are examples of reduction to practice of the present invention and confirmation that the principles described in the present invention are therefore valid but should not be construed as in any way limiting the scope of the invention.
Textile surfaces were treated with a solution comprising 1.75% w/v of 8-HQ and 1.75% BIT, or their derivatives, in 80 mL of acetone. In a separate solution, 4 mL of tetramethyl orthosilicate and 10 mL of 0.1 M hydrochloric acid are combined and vortexed for 1 min. The tetramethyl orthosilicate solution was then added to the acetone solution, mixed thoroughly, vortexed, and applied to the dry textile surface. The treated textile surface was heated until cured, such as by either conventional heating at 75° C. or microwave for 45 sec.
Pretreatment chemicals according to embodiments of the present invention were applied to paints and coatings by replacing the pigment component of the paint or coating with a volume of the pretreatment chemical (ranging from 1% w/w to 10% w/w). The paints and coatings were applied to surfaces according to convention methods. Hazardous materials were deactivated when placed in contact with surfaces treated with the paints or coatings.
Cotton samples treated with 8-HQ and BIT were challenged in a headspace permeation experiment against a sarin stimulant, 5 μg of diisopropylfluorophosphate (“DFP”) vapor, as an 80 μg/cm2 total challenge. In
Table 1, below, provides specific data values shown in
Cotton samples were treated with different combinations of 8-HQ/BIT and challenged for 2 hr with 5 μg DFP vapor in a headspace permeation experiment. In
8-HQ treated fabric and controls were tested against a 400 μg/cm2 sample of soman for 5 days. Permeation data, acquired at the Army Edgewood Chemical and Biological Center (Edgewood, Md.), are shown in Table 4, below. Treated fabrics outperformed the controls against the soman agent by approximately 100-fold, which was observable for up to 5 days (arbitrary units).
Table 5 includes data, similar to Table 4, but against a 400 μg/cm2 sample of sulfur mustard agent for 3 days. Treated fabrics outperformed the controls against the sulfur mustard agent by approximately 10-fold, which was observed for up to 3 days (arbitrary units).
Table 6 includes data, similar to Tables 4 and 5, but against a 400 μg/cm2 sample of DFP for 2 days. Treated fabrics outperformed the controls against the DFP agent by approximately 10-20-fold, which was observed for up to 2 days (arbitrary units).
Table 7 summarized direct liquid deposition testing on the fabrics tested in this Example 7. Treated fabrics performed significantly better than controls against all three agents (arbitrary units).
While the present invention has been illustrated by a description of one or more embodiments thereof and while these embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.
This application is a continuation of U.S. application Ser. No. 14/029,952, SELECT SCHIFF BASE COMPOUNDS FOR CHEMICAL AGENT DETOXIFICATION, filed Sep. 18, 2013. The disclosure of the prior-filed application is expressly incorporated herein by references, in its entirety.
The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
| Number | Name | Date | Kind |
|---|---|---|---|
| 10118060 | Owens | Nov 2018 | B2 |
| Entry |
|---|
| United States Patent and Trademark Office, Non-Final Office Action in U.S. Appl. No. 14/029,952, dated Jun. 19, 2018, 6 pages total. |
| Number | Date | Country | |
|---|---|---|---|
| 20180193682 A1 | Jul 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14029952 | Sep 2013 | US |
| Child | 15878573 | US |
