WO2008051179A2

WO2008051179A2 - Protective fabrics with catalytic neutralization properties

Info

Publication number: WO2008051179A2
Application number: PCT/US2006/020160
Authority: WO
Inventors: Edward P. Locke
Original assignee: K & M Environmental, Inc., D/B/A Morphix Technologies
Priority date: 2005-06-06
Filing date: 2006-05-24
Publication date: 2008-05-02
Also published as: WO2008051179A3

Abstract

A protective material (10) includes, in an exemplary embodiment, at least one of a woven fabric, a non-woven fabric, and a foam which incorporates at least one neutralization chemical compound. The at least one chemical compound functions catalytically through consumption of ubiquitous ambient constituents or pseudo-catalytically through consumption of additives which regenerate the reactive detoxifying moiety.

Description

PROTECTIVE FABRICS WITH CATALYTIC NEUTRALIZATION PROPERTIES

BACKGROUND OF THE INVENTION

[0001] This invention relates generally to protective materials to protect from chemical and biological agents, and more particularly, protective fabrics having catalytic neutralization properties that can be used to make protective clothing, protective enclosures, filtration media, and other embodiments.

[0002] State-of-the-art Chemical-Biological (CB) protective Level A suits in use today by civilians and first responders are constructed from technologically advanced polymeric materials such as Tychem^® or Tyvek^®. These multiply nonwoven laminates generally consist of one or more layers of low density polyolefin, ethylene vinyl acetate, and modified poly(vinyl chloride) (e.g. Saranex^®) with optional added UV stabilizers (Tinuvin™, Chimasorb™) and fire retardants (inorganic salts, phosphine oxides, NFP etc.). Importantly, these materials are specifically engineered to be impermeable to chemical vapors including water vapor. Breathability or mass transfer of water vapor from "inside-out" is a challenging problem from the perspective of garment wearability. While these materials possess superior CB resistance through their ability to block the permeation of these agents, it is their inherent protective properties that present severe wearability limitations. An individual wearing these garments under even mild exertion conditions will become overheated quickly due to inhibition of natural evaporative cooling (perspiration) mechanisms, thus providing significant time limitations on users in hostile environments.

BRIEF DESCRIPTION OF THE INVENTION

[0003] In one aspect a protective material is provided. The protective material includes at least one of a woven fabric, a non-woven fabric, and a foam which incorporates at least one neutralization chemical moiety. The neutralization chemical moiety functions catalytically through consumption of ubiquitous ambient constituents or pseudo-catalytically through consumption of additives which regenerate the reactive detoxifying moiety.

[0004] In another aspect, a multi layered protective material is provided. The protective material includes a base layer that is formed from at least one of a woven fabric, a non-woven fabric, and a foam. At least one neutralization chemical compound is incorporated into the base layer. A hydrophobic layer can be applied to a first surface of the base layer. The hydrophobic layer is formed by a hydrophobic porous membrane and/or coating. A hydrophilic layer can be applied to a second surface of the base layer. The hydrophilic layer is formed from a hydrophilic polymer membrane and/or coating. The at least one neutralization chemical compound functions catalytically through consumption of ubiquitous ambient constituents or pseudo-catalytically through consumption of additives which regenerate the reactive detoxifying moiety.

BRIEF DESCRIPTION OF THE DRAWINGS

[0005] Figure 1 is an exploded schematic illustration of a multi layered protective material in accordance with an exemplary embodiment of the present invention.

[0006] Figure 2 illustrates various mechanisms of covalent dye attachment.

[0007] Figure 3 shows the reflectance spectrum of a cotton swatch which was functionalized with a colorimetric chemistry responsive to alkylating agents.

[0008] Figure 4 shows chemical structures of exemplary CWAs, TIMs, and toxins.

[0009] Figure 5 shows a table of chemical agent classifications. [0010] Figure 6 illustrates hydrolytic pathways and byproducts of exemplary CWAs.

[0011] Figure 7 illustrates exemplary neutralizing moieties for nerve and alkylating agents.

[0012] Figure 8 illustrates tandem chemistry for neutralization of nerve agents and subsequent neutralization of HF byproduct.

[0013] Figure 9 illustrates oxidative doping of polyaniline by protic acids.

[0014] Figure 10 illustrates exemplary antireductant molecules for the multi layered protective material illustrated in Figure 1.

[0015] Figure 11 shows table of biological agents and relevant parameters.

[0016] Figure 12 illustrates Cu(II)tren artificial peptidase

DETAILED DESCRIPTION OF THE INVENTION

[0017] Smart garment protective materials which include novel chemical technologies capable of catalytically detoxifying chemical and biological agent vapors and aerosols via chemical degradation mechanisms are described below in detail. Many chemical warfare agents produce harmful secondary threats upon chemical degradation. The protective materials include tandem chemistries to simultaneously address the neutralization of both the primary agent and any of its toxic secondary degradation products. Catalytic and pseudo-catalytic neutralization technologies facilitate long-term neutralization capacities toward various agent hazards in CB garments, thus enabling the user to work for extended periods of time in a contaminated area without heat exhaustion or a very limited agent capacity threshold. Catalytic neutralization is defined here as the ability of one reactive chemical moiety to undergo several iterations of detoxifying chemical reactions with a threat biological or chemical agent by virtue of consuming only ambient constituents (e.g. air, moisture, light, etc.) to allow catalytic cycling and regeneration of the reactive moiety. Pseudo-catalytic neutralization is defined here as the ability of one reactive chemical moiety to undergo several iterations of detoxifying chemical reactions with a threat biological or chemical agent by virtue of consuming an additional chemical constituent which is capable of regenerating the reactive moiety while being consumed in the process. Both of these approaches permit the simultaneous features of efficient agent neutralization and fabric breathability.

[0018] The inorganic and organic neutralization chemistries described below when applied to materials used to make protective clothing, protective enclosures, filtration media, and other embodiments are capable of rapid detoxification (on the order of seconds) of harmful agents. Neutralizing chemistries can be introduced into various garment or other embodiment materials through processes of doping, salt complex formation (mordanting), hydrogen bonding, and true covalent attachment. Materials which lend themselves to these processes include cotton, nylon, polyesters, polyacrylonitrile, and polyurethanes. Additionally, these materials can be processed into woven garments, foamed (non-woven) garments, or permeable thin films. Composite structures of these materials with other breathable hydrophobic or hydrophilic materials along with liner and adhesive materials can then be constructed to give finished garment materials suitable for protective clothing manufacture and finished materials for other embodiments, for example, protective enclosures, filtration media, and the like. Such protective materials can be useful in a multitude of embodiments used by military personnel, medical personnel, first responders, and normal citizens

[0019] Referring to the drawings, Figure 1 is an exploded sectional schematic illustration of a multi layered protective material 10 in accordance with an exemplary embodiment of the present invention. Protective garment material 10 includes a base layer 12 that is formed from at least one of a woven fabric, a non- woven fabric, and a foam. At least one neutralization chemical compound is incorporated into the base layer. Base layer 12 includes a first surface 14 and a second surface 16. First surface 14 is an outwardly facing surface and second surface 16 is an inwardly facing surface when protective material 10 is formed into a finished protective embodiment, for example, a protective garment (not shown).

[0020] A high-strength, porous hydrophobic layer 18 is bonded to first surface 14. Hydrophobic layer 18 is formed, in the exemplary embodiment, from a porous hydrophobic membrane. In alternate embodiments, layer 18 is formed from a porous hydrophobic coating, or a porous membrane coated with a hydrophobic coating. Hydrophobic layer 18 permits water vapor to pass through to the outside environment, for example, perspiration, to pass through from a user wearing a garment made from protective material 10 to the outside environment. At the same time, hydrophobic layer 18 repels macroscopic water droplets in the outside environment to prevent the water from passing through protective material 10 onto the user.

[0021] A porous hydrophilic layer 20 is bonded to second surface 16 of protective material 10. Hydrophilic layer 20 is formed, in the exemplary embodiment from a porous hydrophilic membrane. In an alternate embodiment, hydrophilic layer 20 is formed from a porous membrane coated with a hydrophilic coating. Hydrophilic layer 20 permits water vapor to pass through to the outside environment, for example, perspiration from a user wearing a garment made from protective material 10 to pass through the outside environment.

[0022] A porous liner layer 22 is bonded to hydrophilic layer 20. Liner layer 22 can be made from any suitable material, for example, Tricot fabrics such as nylon and polyester. In alternate embodiments, another porous hydrophobic layer (not shown) is positioned between liner layer 22 and hydrophilic layer 20 to enhance water vapor mass transfer away from the user's body.

[0023] Functionalized base layer 12 for agent neutralization can be produced, for example, using methodologies for dyeing and modification of several textile materials including nylon, cotton, and polyester, and additionally conductive polymers including polyaniline, polythiophene and polypyrrole. Table 1 shows a number of industrial methods commonly used for dyeing of the more widely used textile materials. Table 1 shows relevant covalent methods of dyeing which are of use in making base layer 12. Polyamides, for example, nylon, and cellulose (cotton) lend themselves to several different covalent dyeing methods. Figure 2 shows generically the molecular interactions between dye and substrate responsible for covalent attachment (fastness) of dyes using four different methods from Table 1. The disazo chemistry is a method which takes advantage of additive hydrogen bond strengths and molecular recognition phenomena. This method results in fast dyes on cellulose materials provided the proper choices of dye and dyeing conditions are made.

TABLE l

* covalent dyeing method

[0024] Figure 3 shows the reflectance spectrum of a cotton swatch which was functionalized with a colorimetric chemistry responsive to alkylating agents. The colorimetric component was attached to the cotton structure using a disazo dyeing technique. The attached chemistry was fast to washing repeatedly with water and the solvent used originally to incorporate the chemistry. The swatch was exposed to the static vapors of methyl chloro formate (23 ⁰C, 45% RH) for a total of 3 seconds and visible reflectance spectra were acquired at 1 second intervals. The cotton swatch undergoes a remarkably fast color change from pale yellow to deep red. Based on mechanistic considerations, this colorimetric response correlates with detoxification of the chemical agent. Importantly, the detoxification mechanism is not specific to methyl chloroformate, but applies broadly to agents capable of alkylating nucleophiles. Thus, these and other related chemistries can serve as a broad chemical class of detoxifying materials and can be used to neutralize known alkylating agents, for example the alkylating agents shown in Figure 5.

[0025] For the purpose of developing broad-spectrum neutralization chemistries, the chemical warfare agents (CWAs) and toxic industrial materials (TIMs) can be grouped into classes according to their reactivity profile (see Figures 4 and 5). As shown in Figure 4, a substantial portion of the high risk agents can be classified as alkylating agents. Furthermore, many of these alkylating agents produce acidic TIMs (Brønsted acids) upon hydrolysis. Most of the known methods of decontamination (water, hypochlorite, peroxide, ozone) produce these acids as byproducts of the "decontamination" process. It is important to note that effective neutralization chemistries should possess the ability to disarm the agent and neutralize the acid byproduct of the disarming step.

[0026] The most probable degradation mechanism for nerve and alkylating agents is hydrolysis. The differing hydrolysis rates for these agents have important implications on their efficacy as chemical weapons from the standpoint of environmental stability. Generally speaking, the more persistent agents hydrolyze at much slower rates, thus allowing them to retain toxicity for long periods under ambient humidity levels. However, even upon hydrolysis under ambient conditions, many of these agents release Brønsted acid byproducts which are extremely hazardous TIMs and can pose a significant secondary threat to the user of a protective garment, for example, a first responder, and military personnel. Therefore, neutralizing/self-decontaminating materials can use catalytic neutralization mechanisms coupled with acid byproduct quenching capabilities to overcome these problems. Figure 6 illustrates the hydrolysis/neutralization reactions of Sarin, phosgene, and Tabun to illustrate this point. In this context, the hydrolysis reaction is equated to a neutralization event to produce the secondary threat agents hydrogen fluoride, hydrogen chloride, and hydrogen cyanide, respectively. Methylphosphonic acid (MPA) and phosphoric acid are of low toxicity (LD₅₀ >5g/kg in mammalian systems) and therefore of little concern. Thus, for example, a neutralization garment made from protective material 10 is capable of rapid agent neutralization and subsequent quenching of the harmful acidic byproducts. An exemplary garment made from protective material 10 which supports these chemical events via a catalytic or pseudocatalytic mechanism provides enhanced protection to the civilian, first responder, medical personnel, and military personnel in dangerous environments for short or extended periods of time.

[0027] A number of different chemistries can serve as functional materials for the catalytic neutralization of nerve and alkylating agents shown in Figure 7. Criteria for choosing these chemistries included high nucleophilicity, predicted formation of labile intermediates upon reaction with agent to allow for catalytic cycling, and literature precedent for functionalized derivatives which will facilitate the use of these chemistries in covalent modification strategies.

[0028] An example of a tandem chemistry embodiment for nerve agent neutralization is shown in Figure 8. 4-Dimethylaminopyridine (DMAP) is an extremely good nucleophile and is used widely in organic synthesis as a hypernucleophilic agent. A polymer and fabric-tetherable derivative of DMAP is covalently attached to fibers, film, woven, or nonwoven material of base layer 12 to give a neutralizing garment/film. Reaction of this material with Sarin proceeds as shown in Figure 8 to give a labile pyridinium intermediate which undergoes facile hydrolysis (ambient moisture from atmosphere and mass transfer from body) to produce the non-toxic IMPA and the pyridinium hydrofluoride byproduct shown. As described below, an acid scavenging material, for example, dopable conductive polymers, functionalized amino acids, carbonate salts, and the like, consumes the harmful HF byproduct to regenerate the pyridine nucleus and complete the catalytic cycle. Employing this neutralizing approach, protective material 10 can be manufactured to include polymer film on film laminates, foamed polymer blends of conductive and functionalized materials, or functionalized conductive polymers derived through chemical synthesis from functionalized monomers.

[0029] As shown in Figure 8, protic acid byproducts with significant toxicity are produced upon hydrolysis or neutralization of nerve agents and many of the CWAs. These Brønsted acids must be neutralized as well if a CB garment or other embodiment is going to be useful in the field. Several approaches to deal with acid neutralization are viable. Both approaches involve quenching of the acid species but differ mechanistically due to the difference in the relative strengths of the acid byproducts.

[0030] The stronger acids (HCl, H₂SO4, HNO₃, HF) readily dope nonconductive forms of electrically conductive polymers such as polyaniline emeraldine base (PANl-EB) and polypyrrole (Ppyr). In the absence of reducing equivalents, this doping is essentially non-reversible, and thus can thermodynamically drive reactions producing these acids to completion based on LeChatlier's Principle. The doping mechanism of polyaniline is shown in Figure 9. Protonation of the insulating PANI-EB results in a net oxidation of the polymer to a quinoidal/radical cation structure known as polyaniline emeraldine salt (PANI-ES) which is electrically conductive. This acid doping of PANI can take place rapidly (several minutes) in solution and vapor atmospheres. Incorporation of this material as a standalone film barrier or as a component of a catalytic neutralizing film barrier produces an effective quenching material for the strong acid byproducts and TIM acids.

[0031] PANI derivatives with increased organic solubility have been studied extensively. The syntheses of PANI derivatives are straightforward and lend themselves to fabric functionalization technologies. Synthesis of ethoxy-PANI can be adapted to facilitate oxidative synthesis of PANI directly on fabric via preliminary attachment of cellulosic hydroxyl functionalities to the aniline nucleus prior to polymerization. Soluble Boc-PANI is a useful material for this application in that the acid-labile Boc protecting group serves to quench one equivalent of protic acid and the ensuing liberated PANI-EB then is capable of consuming another equivalent of acid upon oxidation to PANI-ES.

[0032] Among the oxidants listed in Figure 5, chlorine is considered to be a high risk TIM. This powerful oxidant and the others listed are capable of oxidizing the reduced forms of conducting polymers such as PANI-EB, polythiophene, polyethylenedioxy thiophene, etc. Oxidative doping of PANI-EB, blends of polyaniline with PVC, and copolymers of polyaniline with polythiophene and polypyrrole through exposure of films of these materials to Cl₂, Br₂, HCl, HBr, bromoacetone, and cyanogen bromide (CK simulant) has been researched.

[0033] The Cu(II)tren peptidase material described below can also serve as a redox active material for the catalytic neutralization of reductants such as hydrides (Arsine, Phosphine) and sulfides (H₂S, carbon disulfide). In biological systems, copper is an extremely important redox catalyst. In the solid state as in a neutralizing garment, the reduced copper would be reoxidized to Cu(II) by ambient oxygen to complete the catalytic cycle.

[0034] A biomimetic approach to detoxify harmful reducing agents is based on the reduction of primaquine, an antimalarial drug whose mechanism of action in vivo involves drug activation by reduction to the dihydropiperidinyl nucleus via NADPH. Following reduction of the primaquine molecule upon exposure to the chemical agent, ambient oxygen serves as the ubiquitous regenerating agent to afford the catalytic cycle as shown in Figure 10. Derivatives of primaquine with reactive tethers are covalently incorporated into fabrics using standard chemistries as described above. Chemical syntheses of primaquine derivatives suitable for further conversion into reactive tether molecular tags are known.

[0035] Another biomimetic approach to reducing agent neutralizion is based on ubiquinone, otherwise known as Coenzyme Q is shown in Figure 10. This lipophilic quinone is a key structure that supports electron transfer in the mitochondrial respiratory cycle. The long unsaturated side-chain serves to anchor the molecule in the mitochondrial membrane where it accepts two electrons from NADPH and transfers them to cytochrome c. Quinones of this nature are readily reduced to their hydroquinone forms by many reducing agents. Derivatives of the quinone which include reactive tethers in place of the unsaturated side-chain to facilitate functionalization of various materials such as nylon, cotton and polyester are prepared via standard synthetic manipulations. As in the case for primaquinone, ambient oxygen is responsible for completing the catalytic cycle through regeneration of the quinone structure.

[0036] Biological weapons derive from several classes of pathogens including bacteria, viruses and rickettsiae. Rickettsiae are intracellular bacteria that possess characteristics of bacteria and viruses. They have cellular machinery similar to bacteria and require oxygen, but can only thrive in living cells. Biological toxins are considered a fourth class in which toxic substances produced by a living organism are responsible for the pathogenicity and not the organisms themselves. Pathogens are good biological warfare agents (BWAs) if they reliably exert high toxicity (or lethality) at low dose levels, are easily manufactured, easily disseminated, and are stable and persistent under ambient conditions. Many of these materials are readily obtained through rudimentary microbiological techniques and thus have the potential to be used in bioterrorist activities and in warfare arenas.

[0037] Relevant to CB protective garments are those agents which are capable of percutaneous infectivity and those that are persistent enough to remain active on clothing or other materials for extended periods of time. In this scenario the likelihood of inhalation, absorption through garment and skin, and secondary exposure of others is high. Figure 11 shows relevant parameters for some high potential threat BWAs. In the context of protection of the civilian and first responder during a release of BWA, only some of these agents are harmful or infectious by the cutaneous route. The last column in the table shown in Figure 11 indicates this property for the agents listed. For example, Anthrax is well known to be infectious through skin contact as well as inhalation. Plague and Yellow Fever are not infectious through direct skin contact but can be disseminated through infected fleas and mosquitoes, respectively. Therefore, it is critical that the civilian and first responder be protected from these carriers by a CB garment containing an effective level of insect repellent. On the other hand, Tularemia is highly infectious through the cutaneous, aerosol inhalation, and rabbit/tick carrier routes. Additionally, the hemorrhagic Marburg and Ebola viruses have been contracted through direct contact with infected blood and other materials. Smallpox, Q Fever, Botulinum, and Ricin are almost exclusively aerosol inhalation/ingestion hazards during biological warfare events.

[0038] The toxins class of agents are either small molecule toxins or polypeptide toxins. The small molecule toxins can act non-selectively as blistering agents and can also act at specific loci in biological systems as part of their bioactivity spectrum. However, botulinum and ricin toxins have no inherently corrosive component (e.g., epoxy moiety) but rather act at specific loci in cells to inhibit protein synthesis.

[0039] For example, the trichothecene fungal metabolites are extremely effective blister agents and are several-fold more toxic than HD. Of the biological agents, these mycotoxins are of significant concern as primary acting cutaneous agents during biowarfare incidents. T-2 toxin has been implicated in Indo- China yellow rain. The chemical structure of T-2 toxin is shown in Figure 4. The toxicity of these materials is mostly associated with the epoxide moiety, which serves as a potent alkylating group.

[0040] The Botulinum toxin is a 1300 amino acid residue polypeptide. Ricin is a dimeric protein with a molecular weight of ~ 60,000 kiloDaltons. Garments with the capability of neutralizing these polypeptide toxins include an agent binding event followed by a chemical event which destroys the specific chemical structure in the toxin molecule responsible for its toxicity profile. For these toxins, the specific chemical structure is the peptide sequence. Therefore, disrupting that sequence at several locations through a peptide hydrolysis mechanism renders the material harmless.

[0041] According to the fabric functionalization described above, artificial peptidase containing protective materials 10 are capable of rapid polyamide hydrolysis under ambient conditions and can serve as neutralizing materials for these toxins. Rapid catalytic peptidase activity in a number of functionalized materials based on crosslinked polystyrene and polyethyleneimine has been shown. Of particular interest is the Cu(II)tren containing artificial metallopeptidase as shown in Figure 12. This material has the ability to hydrolyze peptide amide bonds at room temperature and neutral pH and should neutralize botulinum and ricin toxins in a catalytic fashion. Additionally, because the polymeric material contains Cu(II) has positive implications on the material's ability to neutralize some or all of the other biological agents and many of the CWAs and TlMs. This synergy of activities supports combining select chemistries in garment constructs, protective enclosure constructs, filtration media constructs, and the like, which offer broad chemical and biological agent neutralization capabilities. Copper chelate complexes derived from numerous chelating groups can be doped into protective materials or they can be prepared with tethers for covalent attachment to finished embodiments, for example, to garments, to protective enclosures, to filtration media, and the like. All of these materials have potential biocidal and chemical neutralizing capabilities and are suitable for use in making protective material 10.

[0042] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.

Claims

WHAT IS CLAIMED IS:

1. A protective material comprising:

a base layer having a first surface and an opposing second surface, and comprising at least one of a woven fabric, a non-woven fabric, and a foam;

at least one reactive neutralization chemical moiety incorporated into said base layer;

each said reactive neutralization chemical moiety functions catalytically through consumption of ambient constituents or pseudo-catalytically through consumption of additives which regenerate the reactive neutralization moiety.

2. A protective material in accordance with Claim 1 further comprising a porous hydrophobic layer bonded to said first surface of said base layer, said hydrophobic layer comprising at least one of a porous hydrophobic membrane and a porous hydrophobic coating.

3. A protective material in accordance with Claim 2 wherein said porous hydrophobic layer comprises a plurality of pores sized to permit water vapor to pass through said porous hydrophobic layer and to repel macroscopic water droplets to prevent the water droplets from passing through said porous hydrophobic layer.

4. A protective material in accordance with Claim 1 further comprising a porous hydrophilic layer bonded to said second surface of said base layer, said porous hydrophilic layer comprising at least one of a porous hydrophilic membrane and a porous membrane coated with a hydrophilic coating.

5. A protective material in accordance with Claim 4 further comprising a porous liner layer bonded to said porous hydrophilic layer, wherein said porous hydrophilic layer comprises a first surface and an opposing second surface, said first surface of said porous hydrophilic layer is bonded to said second surface of said base layer and said second surface of said porous hydrophilic layer is bonded to said porous liner material.

6. A protective material in accordance with Claim 5 further comprising a porous hydrophobic layer bonded between said second surface of said porous hydrophilic layer and said porous liner layer.

7. A protective material in accordance with Claim 1 wherein said at least one reactive neutralization chemical moiety is capable of neutralizing at least one of a chemical warfare agent, a biological warfare agent, a toxic industrial material, and secondary degradation products of at least one of the chemical warfare agent, the biological warfare agent, and the toxic industrial material.

8. A protective material in accordance with Claim 7 wherein said at least one of a chemical warfare agent, a biological warfare agent, and a toxic industrial material comprises at least one of electrophilic alkylating agents, oxidants, nucleophilic agents, reductants, ligands, Brønsted acids, organic vapors, bacteria vegetative cells and endspores, viruses, and toxins.

9. A protective material in accordance with Claim 7 comprising at least two reactive neutralization chemical moieties wherein a first reactive neutralization chemical moiety is capable of neutralizing at least one of a chemical warfare agent, a biological warfare agent, and a toxic industrial material which creates a secondary degradation product, and a second reactive neutralization chemical moiety is capable of neutralizing said secondary degradation product.

10. A protective material in accordance with Claim 1 wherein said base layer comprises at least one of cottons, nylons, polyesters, polyacylonitriles, polyethers, and polyurethanes.

1 1. A protective material in accordance with Claim 1 wherein said at least one reactive neutralization chemical moiety is incorporated into said base layer by at least one of coating, doping, salt complex formation, hydrogen bonding, and covalent attachment.

12. A protective material comprising:

at least one reactive neutralization chemical compound incorporated into said base layer;

a hydrophobic layer bonded to said first surface of said base layer, said hydrophobic layer comprising at least one of a porous hydrophobic membrane and a porous hydrophobic coating;

each said reactive neutralization chemical compound functions catalytically through consumption of ambient constituents or pseudo-catalytically through consumption of additives which regenerate the reactive neutralization moiety.

13. A protective material in accordance with Claim 12 wherein said porous hydrophobic layer comprises a plurality of pores sized to permit water vapor to pass through said porous hydrophobic layer and to repel macroscopic water droplets to prevent the water droplets from passing through said porous hydrophobic layer.

14. A protective material in accordance with Claim 12 further comprising a porous hydrophilic layer bonded to said second surface of said base layer, said porous hydrophilic layer comprising at least one of a porous hydrophilic membrane and a porous membrane coated with a hydrophilic coating.

15. A protective material in accordance with Claim 14 further comprising a porous liner layer bonded to said porous hydrophilic layer, wherein said porous hydrophilic layer comprises a first surface and an opposing second surface, said first surface of said porous hydrophilic layer is bonded to said second surface of said base layer and said second surface of said porous hydrophilic layer is bonded to said porous liner material.

16. A protective material in accordance with Claim 15 further comprising a porous hydrophobic layer bonded between said second surface of said porous hydrophilic layer and said porous liner layer.

17. A protective material in accordance with Claim 12 wherein said at least one reactive neutralization chemical compound is capable of neutralizing at least one of a chemical warfare agent, a biological warfare agent, a toxic industrial material and secondary degradation products of at least one of the chemical warfare agent, biological warfare agent, and toxic industrial material.

18. A protective material in accordance with Claim 17 wherein said at least one of a chemical warfare agent, a biological warfare agent, and a toxic industrial material comprises at least one of electrophilic alkylating agents, oxidants, nucleophilic agents, reductants, ligands, Brønsted acids, organic vapors, bacteria vegatative cells and endspores, viruses, and toxins.

19. A protective material in accordance with Claim 17 comprising at least two reactive neutralization chemical compounds wherein a first reactive neutralization chemical compound is capable of neutralizing at least one of a chemical warfare agent, a biological warfare agent, and a toxic industrial material which creates a secondary degradation product, and a second reactive neutralization chemical compound is capable of neutralizing said secondary degradation product.

20. A protective material in accordance with Claim 12 wherein said base layer comprises at least one of cottons, nylons, polyesters, polyacylonitriles, polyethers, and polyurethanes.

21. A protective material in accordance with Claim 12 wherein said at least one reactive neutralization chemical compound is incorporated into said base layer by at least one of coating doping, salt complex formation, hydrogen bonding, and covalent attachment.