WO2017172882A1

WO2017172882A1 - Pyridazine and pyridazinone based foam filtration materials for removal of nucleophiles, electrophiles, and metals

Info

Publication number: WO2017172882A1
Application number: PCT/US2017/024702
Authority: WO
Inventors: Douglas A. LOY; Robb E. BAGGE
Original assignee: University of Arizona; Arizona's Public Universities
Current assignee: University of Arizona; Arizona's Public Universities
Priority date: 2016-03-29
Filing date: 2017-03-29
Publication date: 2017-10-05
Anticipated expiration: 2018-09-29

Abstract

Pyridazine and pyridazinone based foams synthesized using a Carboni-Lindsey reaction. These foams can be manufactured from cheap starting materials and are effective removal of both nucleophilic and electrophiiic chemicals, harmful substances, and metals. The foams can be used as a colorimetric indicator to determine level of exposure to harmful substances. Applications of said foams include lab safety, odor control, chemical warfare agent filtration, and mine safety.

Description

PYRIDAZINE AND PYRIDAZI QNE BASED FOAM FILTRATION MATERIALS FOR REMOVAL OF UCLEOPHILES, ELECTROPHILES, AND METALS

CROSS REFERENCE

fOOOl] This application claims priority to U.S. Patent Application No, 62/314,813, filed March 29, 2016, the specification(s) of which is/are incorporated herein in their entirety by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to pyridazine- and pyridazinone-based polymer foams effective for removal of nucleophilic and electrophilic chemicals and metals.

BACKGROUND OF THE INVENTION

[0003] Chemical agents encountered by workers can cause health problems such as occupational asthma, nasal and sinus allergies, hives, and in some cases, anaphylactic reactions. The World Health Organization has ranked respiratory disease as one of the top six workplace ailments; therefore many companies have invested in respiratory protection devices for filtering out harmful substances, such as respiratory sensitizers, to reduce worker exposure. Due to the high costs of said protection devices, some employers may limit the number of available devices to the workers despite workplace regulations. Hence, there is a need to develop filtration materials in a cost-effective and economical manner. Other applications that would benefit from low-cost filtration materials include water treatment, biosolids drying, odor control such as uptake of hydrogen sulfides and ammonia compounds, filtration systems, respiratory protection from chemical warfare agents, and lab and industry safety. The present invention resolves this need by providing for novel polymer foams and cost-effective methods of making such foams.

SUMMARY OF THE INVENTION

[0004] Pyridazine and pyridazinone based polymer foam synthesized from a Carboni- Lindsey reaction between substituted tetrazine species and polydienes can be used for the effective removal of both electrophilic and nucleophilic chemicals, as well as metals, in their gaseous, liquid and solid states. Examples of polydienes include, but are not limited to, poiybutadiene, polyisoprene, and polychloroprene, !n one embodiment, a foam generated by the reaction of a tetrazine having a ieaving group substitution and a polydiene creates an open-celled porous network which contains reactive sights to trap nucieophilic species (i.e. alkoxides, amines, sulfides, and hydrogen sulfides). In another embodiment, the substituted tetrazine may be reacted with an alkene-containing polymer to generate a foam. In yet another embodiment, the substituted tetrazine may be reacted with an alkyne-containing polymer to generate a foam.

[0005] In some embodiments, the foam materia! can advantageously change color upon reaction with nucieophilic species and be used as a coiorimetric indicator for determining exposure levels to these species. In other embodiments, the material can be modified to filter eiectrophilic species and sequester carbon dioxide and metals, such as mercury, by reacting the foams with amines (ammonia, diamines, multi-amine organics) and/or hydrogen sulfides. Another advantage of the present invention is that it is capable of being produced using low-cost starting materials. Further still, the synthesized material can be porous and sponge-like such that it is capable of taking up many different compounds. Moreover, the present invention may be used in many applications including, but not limited to, lab safety, odor control (water treatment systems, uptake of hydrogen sulfides and amines), chemical warfare agent filtration, and mine safety. None of the presently known prior references or work has the unique inventive technical feature of the present invention.

[0006] Any feature or combination of features described herein are included within the scope of the present invention provided that the features included in any such combination are not mutually inconsistent as will be apparent from the context, this specification, and the knowledge of one of ordinary skill in the art. Additional advantages and aspects of the present invention are apparent in the following detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The features and advantages of the present invention will become apparent from a consideration of the following detailed description presented in connection with the accompanying drawing in which:

[0008] FIG. 1 shows a reaction schematic for the post-functionaiization of foams and nucleophile trapping. Pyridazine substituents can be altered after formation through exposure to a liquid or gaseous nucleophile. Foam samples before and after trapping an amine illustrate the colorimetric indication of the foam,

DESCRIPTION OF PREFERRED EMBODIMENTS

[0009] As used herein, the term "harmful substance" may refer to a substance that is toxic to mammals, e.g. human, and that may cause infections or allergic reactions when exposed to said substance. The harmful substances may be contained is a medium such as dust, gasses, or fumes that may be inhaled, or liquids that are consumed, or fluids, gels, or powders that come into direct contact with a person's body.

[0010] As used herein, the haiides may refer to carcinogenic alkylating agents such as, for example, mustards, alkyi haiides, benzyl haiides, and ally! haiides.

[0011] As used herein, the metals may be any metal cationic species. The metals may have enhanced activity with a dicationic or tricationic main group, transition metals, or f- block metals. The metals can include zero valent, monovalent, and multivalent metals. Also, the metals can be radioactive and nonradioactive. The metal may be from any group of the periodic table for example, a transition metal, an alkali or alkaline earth, a heavy metal, or a rare earth metal. Specific metals can include, but are not limited to: copper (Cu), nickel (Ni), zinc (Zn), lead (Pb), mercury (Hg), cadmium (Cd), silver (Ag), iron (Fe), manganese (Mn), palladium (Pd), platinum (Pt), strontium (St), selenium (Se), arsenic (As), cobalt (Co), tungsten (W), and gold (Au). The transition metal may be a base metal active as a catalyst or catalyst promoter such as Ni, Co or W. In some embodiments, the metal may be contaminants such as various copper, nickel, zinc, cobalt, chromium, and iron species,

[0012] As known to one of ordinary skill in the art, the term "nucleophile" refers to a molecule or ion that donates a pair of electrons to form a new covalent bond. A nucleophile is also known as a Lewis base. An electrophile is a molecule or ion that accepts a pair of electrons to make a new covalent bond. An electrophile is also known as a Lewis acid.

[0013] As used herein, the term "chelate" refers to the formation of a heterocyclic ring containing a metal ion attached by coordinate bonds to at least two nonmetai ions. [0014] According to one embodiment, the present invention utilizes polymers to remove nucleophiles and electrophiles by chemically reacting them with reactive functional groups in polymers bearing dihydropyridazine or dihydropyridazinone substituents. In some embodiments, the iminyi groups with halide or amine leaving groups of the dihydropyridazine or dihydropyridazinone can react with nucleophiles. In other embodiments, the electrophile scavenging materials can have pendant nucleophilic or Lewis base groups placed through modification of the tetrazine-precursor or the dihydropyridazine-modified polymer with a nucleophilic species.

[0015] In one embodiment of the present invention, a polymer filtration material for scavenging a nucleophile, an electrophile, or a metal from a medium is prepared from a polymer backbone having a plurality of alkene functional groups, and a plurality of tetrazine monomers, each having at least one leaving group. Without wishing to limit the invention to a particular theory or mechanism, each tetrazine monomer can react with one of the alkene functional groups of the polymer backbone via a Carboni-Lindsey reaction, thereby forming a pyridazine moiety attached to the polymer backbone. In a preferred embodiment, the polymer filtration material is in the form of a foam.

[0016] In another embodiment, the present invention features a method of producing a polymer filtration material for scavenging a nucleophile, an electrophile, or a metal from a medium. The method may comprise providing a polymer backbone having a plurality of alkene functional groups, providing a plurality of tetrazine monomers, each tetrazine monomer having at least one leaving group, and reacting the tetrazine monomers with the polymer backbone. Without wishing to limit the invention to a particular theory or mechanism, each tetrazine monomer reacts with one of alkene functional groups of the polymer backbone via a Carboni-Lindsey reaction to form a pyridazine moiety attached to the polymer backbone, thereby producing the polymer filtration material. Preferably, the polymer filtration material is in the form of a foam. In some embodiments, the polymer filtration material is formed in about 30 minutes to 1 hour of reacting the tetrazine monomers with the polymer backbone. In some embodiments, the method may be performed at a temperature range of about 10°C to 40°C.

[0017] Again, without wishing to limit the invention to a particular theory or mechanism, at least one equivalent of nitrogen gas can be produced during the reaction of the tetrazine and the polymer backbone for every equivalent of tetrazine used. In the present invention, a carbon dioxide gas is not produced during the reaction of a tetrazine component and a polymeric component unlike during the production of poiyurethane. Therefore, the polymer filtration material formed can be considered as a greener material than polyurethanes, and the resulting foams provide an alternative to polyurethanes.

[0018] In one embodiment, the polymer backbone may be a polydiene, a poiybutadiene, a polyisoprene, or a poiychioroprene. Non-limiting examples of the polymer backbone are as follows:

where n = 5-10,000, m = 5-10,000, and q = 5-10,000.

[0019] In another embodiment, the pyridazine moiety may be a dihydropyridazine or a dihydropyridazinone. In yet another embodiment, the leaving group may be a halide, trifiuoromethanesulfonate, tosylate, amine, diamine, pyrazole, hydrazine, thiol, ester, carboxylate, heteroaromatic, phenyl, alkyi ether, or thioether. In a further embodiment, the tetrazine monomer may further comprise a second leaving group or an unreactive group.

[0020] In one embodiment, the tetrazine monomer may be according to the following:

where Ri is a halide, trifiuoromethanesulfonate, tosylate, amine, diamine, pyrazole, hydrazine, thiol, ester, carboxylate, heteroaromatic, phenyl, alky! ether, or thioether, and where f¾ is a second leaving group or an unreactive group.

[0021] In another preferred embodiment, the polymer filtration material has a colorimetric indication such that the polymer filtration material can change color when capturing the nucleophile, the electrophile, or the metal from the medium. Furthermore, the colorimetric indicator may be effective to determine a level of exposure to the metals, the electrophiiic chemicals, or the nucleophilic chemicals. In some embodiments, the medium is in a gaseous, liquid, or solid state.

[0022] According to another embodiment, the present invention features a method of removing a nucleophilic, electrophilic, or metal contaminant from a medium. The method may comprise contacting the medium with any one of the polymer filtration materials described herein.

[0023] In yet another embodiment, the present invention features a method of removing odors emanating from a medium, such as air or aqueous waste streams. The method may comprise contacting the medium with any one of the polymer filtration materials described herein.

[0024] In a further embodiment, the present invention features a method of removing chemical warfare agents from a medium, such as air or potable water. The method may comprise contacting the medium with any one of the polymer filtration materials described herein.

[0025] According to one embodiment of the present invention, a nucleophile scavenging reagent, also referred to herein as a nucleophile getter, may be a polymer prepared by reacting tetrazines with alkenyl bonds of polymers to form a dihydropyridazine group that can react with nucleophilic species. Non-limiting examples of preparing the polymer are shown in Schemes 1 -3. Preferably, for iminyi based systems, there may be at least one fluoride, chloride, bromide, iodide, trifluoromethanesulfonate (trifiate), tosylate, or amine group, such as a dimethyl pyrazole, on the tetrazine precursor. A second substituenf may be a halide (i.e. F, CI, Br, I, Ts, Tf), an amine, or an unreactive group, such aryls, aikyls, aikenyls, ethers, thiol ethers, esters, amides, or cyanides.

[0026] Scheme 1 . Non-limiting example of a reaction schematic for synthesizing filtration materials. Examples of R include, but are not limited to, halides, pyrazoies, hydrazines, amines, diamines, thiols, esters, carboxylates, heteroaromatics, phenyls, aikyl ethers, and thioethers.

[0027] Scheme 2. Non-limiting example for synthesizing filtration materials usinc dichlorotetrazine and polyisoprene.

[0028] Scheme 3. Non-limiting example for synthesizing filtration materials usinc dichlorotetrazine and polybutadiene.

[0029] In some preferred embodiments, the leaving group is configured to react with the nucleophiie or the electrophile, thereby removing the nucleophiie or the electrophile from the medium. For example, the leaving group can undergo a substitution reaction with the nucleophiie or electrophile, thereby forming a nucleophiie or electrophile substituted material. In other embodiments, the nucleophiie or electrophile substituted material is configured to further undergo a substitution reaction with another electrophile or nucleophiie of a second medium, thereby removing the other electrophile or nucleophiie from the second medium.

[0030] In other preferred embodiments, a nitrogen group of the pyridazine moiety, such as the iminyl nitrogen or the enaminyi nitrogen, is configured to react with the nucleophiie or the electrophile, thereby removing the nucleophiie or the electrophile from the medium. Referring to Scheme 4, a nucleophiie can be removed from air or water or solvent by attacking the iminyl group and replacing the haiide or amine group, or by reacting with the iminyl nitrogen or the enaminyi nitrogen, thereby resulting in the nucleophilic group being covaientiy attached to the polymer bearing the scavenging group. Without wishing to limit the invention to a particular theory or mechanism, covaient attachment and scavenging of nucleophiies can change the physical properties of the polymer. For example, in soluble versions of the nucleophiie scavenging polymer, this can lead to precipitation or gelation of the polymer that can assist in sequestration of the nudeophi!es to remove them more effectively from the environment.

[0031] Scheme 4. A non-limiting reaction schematic of nudeophi!ic attack at varying positions on a nucieophi!e getter.

Enaminyl iniin l

iniinyl

|0032] According to another embodiment of the present invention, an electrophiie scavenging reagent, also referred to herein as an electrophiie getter, may be a polymer with dihydropyridazine or dihydropyridazinone groups having a nudeophi!ic or Lewis base groups that can scavenge electrophiles, such as metal ions, alkyi haiides, or carbon dioxide. In some embodiments, as shown in Scheme 5, these electrophiie getters can be prepared by replacing a halide or amine leaving group in the same polymers used for nucieophile getters with groups bearing one or more amines, thiols, thiol ethers, or mixtures thereof. These substitutions can be done in the tetrazines used to prepare the polymers, or in the dihydropyndazine modified polymers. Without wishing to limit the invention to a particular theory or mechanism, binding with electrophiles may also cause physical properties of the polymer to change and can lead to gelation or precipitation, which can further aid in sequestration of the targeted chemical.

[0033] Scheme 5. A non-limiting example of a polymer with a diamine ligand used to intercept alkyi haiides, metals, and acidic gasses such as carbon dioxide, hydrogen sulfide or hydrogen cyanide, according to an embodiment of the present invention.

[0034] In preferred embodiments, the present invention does not use pyridy! groups as a substituent that can scavenge meta! ions or Lewis acids. Pyridyl groups may be used as a second substituent, but they are not necessary for use in trapping chemical species. Moreover, the nitrogen moiety of the pyridyl may be in the meta or para position with respect to the tetrazine, and not necessarily in the ortho position.

[0035] Scheme 6. A non-limiting schematic for the nucleophiie trapping of amines, alkoxides and hydrogen sulfide according to an embodiment of the present invention.

[0036] In some embodiments, as shown in Scheme 7, the solid filtration material is effective to sequester carbon dioxide upon reaction of an amine functional group of the filtration material with an electrophilic carbon atom of the carbon dioxide molecule. The carbon dioxide is sequestered by converting the amine functional group to a carbamic acid functional group. In other embodiments, the solid filtration material functions to filter electrophilic species and traps the electrophilic species by converting the nucleophilic group (such as amines) into isocyanate.

[0037] Scheme 7, A non-limiting schematic representation of carbon dioxide sequestration, and electrophiie and nucieophiie trapping according to an embodiment of the present invention. In some embodiments, n ranges from about 5-10,000, p ranges from about 5-10,000, and m ranges from about 5-10,000.

-2 mi

[0038] In yet other preferred embodiments, the polymer filtration material is further configured to chelate the metal, namely, via the leaving groups or the substituting groups, chelating the metal, thereby removing the metal from the medium. In some other preferred embodiments, the dihydropyridazine or dihydropyridazinone does not participate directly in the metal chelation, i.e. the nitrogen moiety does not form coordinate bonds to the metal. As shown in Scheme 8, at least two leaving groups of the polymer filtration material can chelate the metal.

[0039] Scheme 8. A non-limiting schematic representation of mercury trapping according to an embodiment of the present invention, where n=5-10,000, m=5-10,000, p=5- 10,000, and q=5-10,000.

[0040] In another embodiment, the nucleophile or eiectrophile substituted material can be used to chelate the metal using at least two groups of the nucleophile or eiectrophile substituents, as shown in Scheme 9. The nucleophile or eiectrophile substituted material can form a metal adduct complex with the metal to function as a metal waste collecting sponge.

|0041] Scheme 9, A non-limiting schematic representation of metal waste collection accordin to an embodiment of the present invention.

X - halogen, fcavwx) group

10042] EXAMPLE 1

[0043] The following are non-limiting examples of the foam filtration material of the present invention. Equivalents or substitutes are within the scope of the invention.

[0044] According to one embodiment, the filtration material may be according to any of the following structures:

where Ρ¾, R₄, R,_¾, and R₆ may each be a haiide or any of the leaving groups disclosed herein, and where n = 5-10,000 and q ^~ 5-10,000. [0045] According to another embodiment, the filtration material may be according to any of the following structures:

where R is a halide, pyrazole, hydrazine, amine, diamine, thiol, ester, carboxyiate, heteroaromatic, phenyl, or an alkylated ether, and where n = 5-10,000, q = 5-10,000, p = 5-10,000, and m = 5-10,000.

[0046] In some embodiments, the nucleophile substituted filtration material formed by the nucleophilic substitution reaction of the filtration material may be according to any of the followin structures:

where Nu-i , Nu₂, Nu₃, and Nu₄ may each be a nucleophilic group, and where n = 5- 10,000 and q = 5-10,000. In some embodiments, the nucleophilic groups may be amines, aikoxides, hydroxyls, or thiols.

[0047] Other non-limiting examples of the nucleophile substituted filtration material may be according to any of the following structures:

where n = 5-10,000, m = 5-10,000, p = 5-10,000, and q = 5-10,000.

[0048] In other embodiments, the electrophiie substituted filtration material formed by the electrophilic substitution reaction of the filtration material may be according to any of the following structures:

where Ei, E₂, E₃, and E₄ may each be an electrophi!ic group, and n = 5-10,000 and q = 5-10,000.

[0049] In yet other embodiments, the metal adduct complex formed by the nudeophiie substituted filtration materia! and the metal may be according to any of the following structures:

where Nu-i , Nu2, Nu3, and Nu₄ may each be a nucleophilic group, and where n = 5- 10,000 and q = 5-10,000, and where M-i , M₂, M₃, and M₄ may be any metal ion. In some embodiments, the nucleophilic groups may be amines, alkoxides, hydroxyis, or thiols.

[0050] According to some embodiments the metal adduct complex formed by the electrophile substituted filtration material and the metal comprising at least one or more of the following structures:

where Ei, E₂, E?„ and E₄ may each be an electrophilic group, and n = 5-10,000 and q = 5-10,000, and where M₅, M₆, M₇, and M₈ may be any metal ion.

[0051] EXAMPLE 2

[0052] The following is a non-limiting example of preparing a foam of the present invention. Equivalents or substitutes are within the scope of the invention.

[0053] In one embodiment, the method of making a solid composition may comprise adding a tetrazine component as a diene of the Diels-Alder reaction in a reaction vessel and adding the polymeric component as a dienophiie of the Diels-Alder reaction in the same reaction vessel. Then the tetrazine component and the polymeric component are mixed to generate a foam which functions as a filtration material.

[0054] To a 20 mL plastic weighing cup was added polybutadiene (hydroxy functionalized, 1200 Mn) (0.2714 g, 5.026 x 10 ³ mol) and 3,6-dichloro-1 ,2,4,5-tetrazine (0.1885 g, 1 .249 x 10^~3 mol). The mixture was stirred until the tetrazine was completely dissolved and gas generation was observed in the bright orange, foaming paste. The orange foam continued to rise under an open-air environment at 25 °C for approximately 30 additional minutes before ceasing to grow any further. After 24 hrs, the mass of product after 24 hrs was 0.4202 g (98.9%). Elemental Analysis: C:65.57, H:7.95, N:8.73, 0:5.01 , Cl:1 1.66 FT-IR (ATR, Ss0₂): cm^"1 = 3235.75, 3084.13, 301 1 .00, 2921.41 , 2852.73, 1678.36, 1446.62, 131 1.15, 1220.50, 1 161.98, 1074.08, 969.01 , 914.56, 733.1 1 , 665.26, 629.72, 621 .1 1 , 585.52, 568.52, 531.93, 498.59, 471.64

[0055] EXAMPLE 3

[0056] The following are non-limiting examples of nucleophiie trapping using an embodiment of the present invention. Equivalents or substitutes are within the scope of the invention.

[0057] Po!y(pyridazine-co~butadiene) foam (0.052 g) was immersed in ammonium hydroxide for five minutes during which time its color underwent a change from light peach to dark brown. The foam was removed from the ammonium hydroxide solution and dried before obtaining a final mass (0.053 g). FT-IR (ATR, Si0₂): cm^"1 - 3207.97, 3004.55, 2923.88, 2852.31 , 1680.39, 1446.23, 1409.48, 1310.72, 1252.57, 1217.44, 1 179.96, 1 155.38, 1074.78, 994.93, 969.40, 915.83, 826.28, 744.54, 723.23, 666.64, 625.94, 610.60, 592.06, 568.10, 545.15, 501 .66, 477.84, 433.79, 416.40.

[0058] Poly(pyridazine-co-butadiene) foam material (0.095 g) was placed into a 25 mL beaker. The beaker was then placed into a 250 mL beaker containing ammonium hydroxide (20 mL) which was subsequently covered with parafiim to seal in the gaseous ammonia fumes. After five minutes, the foam's color had changed from a light peach color to dark brown, and the material had no observed change in mass (0.095 g). FT-IIR (ATR, Si0₂): cm^"1 = 3161.48, 3146.40, 3049.62, 3004.55, 2921.16, 2852.31 , 1679.22, 1444.69, 1410.33, 1310.88, 1252.57, 1219.78, 1 160.23, 1075.27, 994.93, 969.14, 915.94, 744.25, 665.84, 625.94, 609.67, 586.96, 571 .29, 500.83, 478.96, 436.46.

[0059] As used herein, the term "about" refers to plus or minus 10% of the referenced number.

[0060] Various modifications of the invention, in addition to those described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fail within the scope of the appended claims. Each reference cited in the present application is incorporated herein by reference in its entirety.

[0061] Although there has been shown and described the preferred embodiment of the present invention, it will be readily apparent to those skilled in the art that modifications may be made thereto which do not exceed the scope of the appended claims, Therefore, the scope of the invention is only to be limited by the following claims. In some embodiments, the figures presented in this patent application are drawn to scale, including the angles, ratios of dimensions, etc. In some embodiments, the figures are representative only and the claims are not limited by the dimensions of the figures. In some embodiments, descriptions of the inventions described herein using the phrase "comprising" includes embodiments that could be described as "consisting of, and as such the written description requirement for claiming one or more embodiments of the present invention using the phrase "consisting of is met

Claims

WHAT IS CLAIMED IS:

1 . A polymer filtration material for scavenging a nucieophi!e, an electrophile, or a metal from a medium, said material prepared from: a. a polymer backbone having a plurality of aikene functional groups; and b. a plurality of tetrazine monomers, each tetrazine monomer having at least one leaving group, wherein each tetrazine monomer reacts with one of the aikene functional groups of the polymer backbone via a Carboni-Lindsey reaction, thereby forming a pyridazine moiety attached to the polymer backbone; wherein the leaving group is configured to react with the nucleophile or the electrophile, thereby removing the nucleophile or the electrophile from the medium, wherein a nitrogen of the pyridazine moiety is configured to react with the nucleophile or the electrophile, thereby removing the nucleophile or the electrophile from the medium, and wherein the polymer filtration material is further configured to chelate the metal, thereby removing the metal from the medium.

2. The polymer filtration material of claim 1 , wherein the polymer backbone is polybutadiene, polyisoprene, or polychioroprene.

3. The polymer filtration material of claim 1 , wherein the pyridazine moiety is a dihydropyridazine or a dihydropyridazinone.

4. The polymer filtration material of claim 1 , wherein the leaving group is a halide, trifluoromethanesulfonate, tosylate, amine, diamine, pyrazole, hydrazine, thiol, ester, carboxylate, heteroaromatic, phenyl, alkyi ether, or thioether ,

5. The polymer filtration material of claim 1 , wherein each tetrazine monomer may further comprise a second leaving group or an unreactive group.

6. The polymer filtration material of claim 1 , wherein the leaving group undergoes a substitution reaction with the nucieophile or electrophiie, thereby forming a nucleophile or electrophiie substituted material,

7. The polymer filtration material of claim 8, wherein the nucleophile or electrophiie substituted material is configured to further undergo a substitution reaction with another electrophiie or nucieophile of a second medium, thereby removing the other electrophiie or nucleophile from the second medium.

8. The polymer filtration material of claim 1 , wherein at least two leaving groups of the polymer filtration material chelate the metal.

9. The polymer filtration material of claim 6, wherein the nucieophile or electrophiie substituted material is further configured to chelate the metal using at least two groups of the nucleophile or electrophiie substituents.

10. The polymer filtration material of claim 1 , wherein the polymer filtration material has a colorimetric indication, wherein the polymer filtration material is configured to change color when capturing the nucieophile, the electrophiie, or the metal from the medium.

1 1 . The polymer filtration material of claim 1 , wherein the polymer filtration material is in the form of a foam.

12. The polymer filtration material of claim 1 , wherein the medium is in a gaseous, liquid, or solid state.

13. A method of removing a nucleophiiic, eiectrophilic, or metal contaminant from a medium, said method comprising contacting the medium with the polymer filtration material according to any one of claims 1 -1 1 .

14. A method of removing odors emanating from a medium, said method comprising contacting the medium with the polymer filtration material according to any one of claims 1 -1 1 .

15. The method of claim 14, wherein the medium is air or aqueous waste streams.

16. A method of removing chemical warfare agents from a medium, said method comprising contacting the medium with the polymer filtration material according to any one of claims 1 -1 1 .

17. The method of claim 16, wherein the medium is air or potable water.

18. A method of producing a polymer filtration material for scavenging a nucleophile, an electrophile, or a metal from a medium, said method comprising:

a. providing a polymer backbone having a plurality of alkene functional groups; b. providing a plurality of tetrazine monomers, each tetrazine monomer having at least one leaving group; and c. reacting the tetrazine monomers with the polymer backbone, wherein each tetrazine monomer reacts with one of the alkene functional groups of the polymer backbone via a Carboni-Lindsey reaction to form a pyridazine moiety attached to the polymer backbone, thereby producing the polymer filtration material; wherein the leaving group is configured to react with the nucleophile or the electrophile, thereby removing the nucleophile or the electrophile from the medium, wherein a nitrogen of the pyridazine moiety is configured to react with the nucleophile or the electrophile, thereby removing the nucleophile or the electrophile from the medium, and wherein the polymer filtration material is further configured to chelate the metal, thereby removing the metal from the medium.

19. The method of claim 18, wherein each tetrazine monomer is according to the following:

wherein Ri is a halide, trifluoromethanesuifonate, tosyiate, amine, diamine, pyrazole, hydrazine, thiol, ester, carboxylate, heteroaromatic, phenyl, alkyl ether, or thioether, and wherein R₂ is a second leaving group or an unreactive group

20. The method of claim 18, wherein the polymer backbone is poiybutadiene, polyisoprene, or polychloroprene.

21 . The method of claim 18, wherein the pyridazine moiety is a dihydropyridazine or a dihydropyridazinone.

22. The method of claim 18, wherein the leaving group is a halide, trifluoromethanesulfonate, tosylate, amine, diamine, pyrazole, hydrazine, thiol, ester, carboxylate, heteroaromatic, phenyl, alkyl ether, or thioether. .

23. The method of claim 18, wherein each tetrazine monomer may further comprise a second leaving group or an unreactive group.

24. The method of claim 18, wherein the leaving group undergoes a substitution reaction with the nucleophile or eiectrophiie, thereby forming a nucleophile or eiectrophiie substituted material.

25. The method of claim 24, wherein the nucleophile or eiectrophiie substituted material is configured to further undergo a substitution reaction with another eiectrophiie or nucleophile of a second medium, thereby removing the other eiectrophiie or nucleophile from the second medium.

28. The method of claim 18, wherein at least two leaving groups of the polymer filtration material chelate the metal.

27. The method of claim 24, wherein the nucleophile or eiectrophiie substituted material is further configured to chelate the metal using at least two groups of the nucleophile or eiectrophiie substituents.

28. The method of claim 18, wherein the polymer filtration material has a colorimetric indication, wherein the polymer filtration material is configured to change color when capturing the nucieophile, the eiectrophiie, or the metal from the medium.

29. The method of claim 18, wherein the polymer filtration material is in the form of a foam.

30. The method of claim 18, wherein the medium is in a gaseous, liquid, or solid state.

31. The method of claim 18, wherein the method is performed at a temperature range of about 10°C to 40°C.

32. The method of claim 18, wherein the polymer filtration material is formed in about 30-80 minutes of reacting the tetrazine monomers with the polymer backbone.