JP5806409B2 - Active polymer filter containing pendant dioxirane - Google Patents

Description

  The present technology relates to active chemical filter compounds for gas and liquid purification.

  The following is provided to help readers understand. None of the information provided or references cited is admitted to be prior art to the present technology.

  There is an increasing worldwide demand for reliable, efficient and low cost air treatment systems in enclosed spaces. Air pollutants include volatile organic compounds (VOC), inorganic / organic particles and biological particles such as bacteria, fungi, and various other biological contaminants, including viruses. . There are many filtration strategies to purify the air, but it suffers from various drawbacks.

  Physical filtration strategies remove most of the particles but are less effective against VOCs. This can also be a breeding place for microorganisms, which impairs the flow rate of air through the filter.

  The electrostatic filtration strategy improves on basic physical filtration and does not further restrict the air flow. However, energy is required to charge the filter. Importantly, electrostatic filtration strategies do not address VOCs and do not kill bacteria. This can therefore be a breeding place for microorganisms.

Photochemical filters generally contain TiO ₂ as an agent for generating singlet oxygen, which can kill microorganisms. Although generally effective and the effective period of TiO ₂ is long, the effective period of active species of the filter, such as singlet oxygen, is very short. Furthermore, the advantageous TiO ₂ reaction rate is limited to a few surfaces.

  Active chemical filtration is effective, but the shelf life may be too short. Furthermore, the filters can be expensive and / or cumbersome to replace or recharge. Other problems are that the active chemicals can be harmful to health (eg, ozone) and / or very slow reaction rates (eg, peroxymonosulfate).

  The present technology provides polymers with pendant dioxirane moieties that are reactive to microorganisms and VOCs and that can oxidize and kill such materials. This is accomplished by placing the polymer in a filter through which contaminated fluids, ie gases or liquids, can pass. As the fluid passes through the filter, at least some of the contaminants can be oxidized by the pendant dioxirane moiety, thereby purifying the fluid and reducing or eliminating the amount of contaminants present in the fluid. .

  In one embodiment, the polymer includes pendant dioxirane moieties. In various embodiments, the pendant dioxirane moiety is generally represented by Formula I or Formula II.

In Formula I, the pendant dioxirane can be part of a side chain that extends off the backbone of the polymer. In Formula II, the pendant dioxirane can be part of the polymer backbone. In formula I above, R ¹ is a bond (ie, absent), alkylene, perhaloalkylene, cycloalkylene, arylene, heteroarylene, heterocyclylene, amino, carbonyl, carboxyl, alkylcarboxy, carboxyalkyl or alkylcarboxyalkyl. R ² can be an electron withdrawing group; R ³ can be hydrogen, alkyl, perhaloalkyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, amino, carbonyl, carboxyl, alkylcarboxy , Carboxyalkyl or alkylcarboxyalkyl.

  In another aspect, a method comprising providing a first polymer comprising an oxo group and reacting the oxo group with a peroxymonosulfate to form a second polymer comprising a pendant dioxirane moiety. Provided.

  In another aspect, an article comprising a polymer comprising a pendant dioxirane moiety is provided. In various embodiments, the article is a gas or liquid filter.

  In a further aspect, there is provided a gas purification method comprising passing a gas through a filter comprising a polymer comprising a pendant dioxirane moiety, wherein the gas comprises a biological contaminant or a chemical contaminant. . In some embodiments, the gas is air.

  In another embodiment, a fluid purification method comprising passing a fluid, such as a liquid or gas, through a filter, wherein the filter comprises a polymer comprising a pendant dioxirane moiety and the fluid is a biological contaminant or chemical. A method is provided that includes a contaminant.

  In another aspect, a method is provided that includes providing a filter comprising a polymer comprising a ketone moiety and converting the ketone moiety to a dioxirane moiety by reacting the polymer with peroxymonosulfate.

  The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the following drawings and detailed description.

  The illustrative embodiments described in the detailed description and claims are not meant to be limiting. Other embodiments may be utilized and other changes may be made without departing from the spirit or scope of the subject matter presented herein.

  The technology is described herein using several definitions, as set forth throughout the specification.

  As used herein, unless otherwise specified, the singular forms “a (a), (an)” and “the (the)” include plural references. Thus, for example, reference to “a cell” includes a plurality of cells, and reference to “a molecule” is a reference to one or more molecules.

  As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent on the context in which it is used. Where the use of a term is not apparent to one of ordinary skill in the art, “about” shall mean up to plus or minus 10% of a particular term, given the context in which it is used.

  Alkyl groups include straight chain, branched chain or cyclic alkyl groups having 1 to 24 carbons or the number of carbons indicated herein. In some embodiments, the alkyl group has 1 to 16 carbon atoms, 1 to 12 carbons, 1 to 8 carbons, or in some embodiments 1 to 6 carbons. Or 1, 2, 3, 4 or 5 carbon atoms. Examples of straight chain alkyl groups include groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. In some embodiments, the alkyl group may be a substituted alkyl group.

  A cycloalkyl group is a cyclic alkyl group having from 3 to 10 carbon atoms. In some embodiments, the cycloalkyl group has 3 to 7 ring members, while in other embodiments, the number of ring carbon atoms is 3 to 5, 3 to 6, or 5 6 or 7 pieces. Cycloalkyl groups further include monocyclic, bicyclic and polycyclic ring systems. Examples of monocyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups. Bicyclic and polycyclic cycloalkyl groups include bridged or fused rings such as, but not limited to, bicyclo [3.2.1] octane, decalinyl and the like. Cycloalkyl groups include rings substituted with straight or branched chain alkyl groups as defined above. In some embodiments, the cycloalkyl group is a substituted cycloalkyl group. Representative substituted alkenyl groups may be mono-substituted or substituted more than once, for example, but not limited to, one by a substituent such as those listed above. Di- or tri-substituted. Representative substituted alkyl groups may be mono-substituted, or may be substituted more than once, for example, but not limited to, one by a substituent such as those listed above. Di- or tri-substituted.

Alkenyl groups include straight and branched chain alkyl groups as defined above except that there is at least one double bond between two carbon atoms. Thus, an alkenyl group has 2 to 24 carbon atoms, generally 2 to 10 carbon atoms, and in some embodiments 2 to 8, 2 to 6 or 2 to 4 carbon atoms Have Examples include, but are not limited to, vinyl, allyl, —CH═CH (CH ₃ ), —CH═C (CH ₃ ) ₂ , —C (CH ₃ ) ═CH ₂ , — _{C (CH 3) = CH (} CH 3), - C (CH 2 CH 3) = CH 2 and the like. Representative substituted alkenyl groups may be mono-substituted or substituted more than once, for example, but not limited to, one by a substituent such as those listed above. Di- or tri-substituted.

The terms “alkylene”, “cycloalkylene” and “alkenylene”, alone or as part of another substituent, are alkyl, cycloalkyl, respectively, as exemplified by —CH ₂ CH ₂ CH ₂ CH ₂ —. Or a divalent radical derived from an alkenyl group. For alkylene, cycloalkylene and alkenylene linking groups, the orientation of the linking group is not indicated.

As used herein, the term “amine” (or “amino”) refers to the —NHR and —NRR ′ groups, where R and R ′ are independently hydrogen or as defined herein. A substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl group as defined. Examples of amino groups include —NH ₂ , methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, benzylamino and the like.

  The term “oxo” refers to a divalent oxygen group. The term includes double bonded oxygens such as those found in carbonyl groups, but as used herein, the term oxo is specifically a form —O that is part of the polymer backbone. -Single-bonded oxygen. Therefore, the oxo group includes an ether bond (—O—), an ester bond (—O—C (O) —), a carbonate bond (—O—C (O) O—), and a carbamate bond (—O—C (O ) NH— or —O—C (O) NR—) and the like.

  “Substituted” is one or more substituents such as lower alkyl (including substituted lower alkyl such as haloalkyl, hydroxyalkyl, aminoalkyl, etc.), aryl (including substituted aryl), Acyl, halogen, hydroxy, amino, alkoxy, alkylamino, acylamino, thioamide, acyloxy, aryloxy, aryloxyalkyl, carboxy, thiol, sulfide, sulfonyl, oxo, both saturated and unsaturated cyclic hydrocarbons (e.g. (Cycloalkyl, cycloalkenyl), a cycloheteroalkyl and the like refers to a chemical group as described herein. These groups may be bonded to any carbon or alkyl, alkenyl, alkynyl, aryl, cycloheteroalkyl, alkylene, alkenylene, alkynylene, arylene, hetero substituent. Furthermore, the substituent may protrude from the carbon chain itself, or may form part thereof.

  The present technology provides polymers with pendant dioxirane moieties that are reactive to microorganisms and VOCs and that can oxidize and kill such materials. In some embodiments, this is accomplished by placing the polymer in a filter through which contaminated fluid, ie, gas or liquid, may pass. The contaminated fluid may contain contaminants such as microorganisms or VOCs. As the fluid passes through the filter, at least a portion of the contaminants may be oxidized by the pendant dioxirane moiety, thereby purifying the fluid and reducing or removing the amount of contaminants present in the fluid.

  In one aspect, a polymer comprising a pendant dioxirane moiety is provided. Dioxiranes are cyclic peroxides that can be prepared by oxidation of the carbonyl group using various peroxycarbonyl species. Pendant dioxiranes may include members of cyclic groups within the polymer backbone (ie, by oxidation of carbonyl groups where carbon atoms are located in the polymer chain), or pendant dioxiranes are part of an organic group. It may be a side chain of the polymer skeleton.

  In one embodiment, the polymer comprises units represented by Formula I or II.

In formula I, the pendant dioxirane is part of a side chain that extends off the backbone of the polymer. In formula II, the pendant dioxirane is part of the polymer backbone. In Formula I, R ¹ is a bond (ie, R ¹ is not present), or R ¹ is alkylene, perhaloalkylene, cycloalkylene, arylene, heteroarylene, heterocyclylene, amino, carbonyl, carboxyl R ² includes an electron withdrawing group; R ³ is H, alkyl, perhaloalkyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, amino, carbonyl, Carboxyl, alkylcarboxy, carboxyalkyl or alkylcarboxyalkyl.

In Formula I, the electron withdrawing group is a —N ⁺ R ⁴ R ⁵ R ⁶ group, a halogen, NO ₂ , C (O) H, a CO ₂ R ⁷ group, an alkoxy group or a perhaloalkyl group, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H, alkyl or cycloalkyl. According to some embodiments, the electron withdrawing group is perfluoroalkyl.

In various embodiments, R ¹ is alkylene, perhaloalkylene, carbonyl, carboxyl, alkylcarboxyl, carboxyalkyl, or alkylcarboxyalkyl.

  The polymer backbone may generally be any polymer that contains a carbonyl group, to which a moiety containing a carbonyl group may be attached. For example, the polymer backbone is polyolefin, polyalkylene terephthalate, polyacrylate, polylactate, polycarbonate, polyester, polysaccharide, polyacetate, polystyrene maleic anhydride, polyurethane, polyamide, polyacrylamide, polymethacrylate, poly (methyl) methacrylate, aramid Or it may be a copolymer of any two or more such polymers.

  In other embodiments, the polymer comprises units represented by Formula III or IV.

In Formulas III and IV, R ¹ is absent (ie, a bond between the polymer backbone and the methylene group of the dioxirane) or R ¹ is alkylene, perhaloalkylene, cycloalkylene, arylene, heteroarylene, heterocyclylene, amino, carbonyl, carboxyl, alkyl carboxylate, carboxyalkyl alkyl or alkyl carboxyalkyl; ^{R 2} is an electron withdrawing group; ^{R 8 is} an -N ^{+ R} 4 R ⁵ or alkyl; ^{R 9} is -N ⁺ R ⁴ R ⁵ or alkyl; each R ⁴ is independently H, alkyl or cycloalkyl; each R ⁵ is independently H, alkyl or cycloalkyl; R ⁶ is H, alkyl or cycloalkyl; R ⁷ is H, alkyl or cycloalkyl It is. Suitable examples of electron withdrawing groups include, but are not limited ^{to, -N + R 4 R 5 R} 6 group, _{halogen, NO 2, C (O)} H, CO 2 R 7 group, an alkoxy group Or a perhaloalkyl group, wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H, alkyl or cycloalkyl. According to some embodiments, the electron withdrawing group of formula III is perfluoroalkyl. According to some embodiments, R ¹ is alkylene, perhaloalkylene, carbonyl, carboxyl, alkylcarboxyl, carboxyalkyl or alkylcarboxyalkyl. In some embodiments of Formula III, R ¹ is absent or R ¹ is C ₁ -C ₆ alkylene or —N ⁺ R ⁴ R ⁵ ; R ² is alkylene, perhaloalkylene, CO ₂ R ^7, or ^-N + ^R 4 ^R 5 is ^{R 6.} In some embodiments of Formula IV, R ⁸ is —N ⁺ R ⁴ R ⁵ or alkyl; R ⁹ is —N ⁺ R ⁴ R ⁵ or alkyl. In some embodiments, the polymer comprises a repeat unit represented by Formula III, R ¹ is absent or is methylene or ethylene; R ² is H, methyl, ethyl, or trimethylammonium. . In some embodiments, the polymer comprises a repeating unit represented by formula IV, R ⁸ is C ₁ -C ₈ alkylene; R ⁹ is —N ⁺ R ⁴ R ⁵ , R ⁴ Is alkyl; R ⁵ is alkyl. In some embodiments, R ⁸ is —N ⁺ R ⁴ R ⁵ ; R ⁹ is —N ⁺ R ⁴ R ⁵ ; R ⁴ is alkyl; R ⁵ is alkyl. .

  The dioxirane portion of the polymer is a highly reactive group, but has a shelf life that is long enough to actually use the dioxirane. As mentioned above, the polymer comprising pendant dioxirane may be generated from a polymer having at least one carbonyl (CO) group. This wide range of options allows the polymer properties to be modified for a wide range of applications.

  For example, to enhance compatibility with various solutions, the polymer may be selected to be either more hydrophilic or more hydrophobic. If the polymer is used to purify an aqueous solution, it may be desirable to have a more hydrophilic polymer containing groups such as carboxyl groups, hydroxyl groups, ethers, amines or ammonium groups. If the polymer is used to purify contaminated oil, the polymer may contain more alkyl or aryl groups to increase the hydrophobicity of the polymer. Furthermore, the ability to use different polymers together makes the intended environment of use very wide and broaden the range of pollutants that are oxidized.

  In another aspect, a method for preparing a polymer having a pendant dioxirane moiety is provided. For example, the method can include providing a first polymer that includes a carbonyl group and contacting the carbonyl group with a peroxymonosulfate to form a second polymer that includes a pendant dioxirane moiety. . The method may include combining the first polymer with a solution containing peroxymonosulfate. In various embodiments, the pendant dioxirane moiety, i.e., the second polymer, is represented by any of formulas I, II, III, or IV above.

  In various embodiments, the first polymer includes polyalkylene terephthalate, polyacrylate, polylactate, polycarbonate, polyester, polysaccharide, polyacetate, polystyrene maleic anhydride, polyurethane, polyamide, polyurea, polyacrylamide, polymethacrylate. , Poly (methyl) methacrylate, aramid, or a copolymer of any two or more such polymers. In some embodiments, the first polymer comprises poly (alkyl-2-ketoalkenoate). In certain embodiments, the poly (alkyl-2-ketoalkenoate) is poly (methyl-2-keto-3-butenoate) or poly (methyl-2-keto-4-pentenoate).

  Suitable peroxymonosulfates include, but are not limited to, such as alkali metal peroxymonosulfates, ammonium peroxymonosulfates, and phosphonium peroxymonosulfates. Exemplary peroxymonosulfates include, but are not limited to, lithium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxymonosulfate, tetramethylammonium peroxymonosulfate, tetraethylammonium peroxymonosulfate, trimethylammonium peroxy Examples include monosulfate, triethylammonium peroxymonosulfate, triisopropylammonium peroxymonosulfate, tetraisopropylammonium peroxymonosulfate and benzyltriphenylphosphonium peroxymonosulfate.

  Peroxymonosulfate oxidizing agents are commercially available, for example, potassium peroxymonosulfate sold under the name OXONE® (DuPont, Wilmington, DE). Other forms of peroxymonosulfate are available with various counterions such as alkali metal cations, alkaline earth metal cations, ammonium cations, tetraalkylammonium cations, and the like. For example, a form of peroxymonosulfate having a tetrabutylammonium cation is commercially available under the name OXONE® tetrabutylammonium salt (Sigma-Aldrich, St. Louis, MO).

  The peroxymonosulfate solution may be prepared from water and the peroxymonosulfate compound at a concentration of about 0.1 millimolar to about 1 molar or, in some examples, about 1 millimolar to about 100 millimolar. In some examples, the peroxymonosulfate solution may include a base or buffer to adjust the pH. The solution may have a pH between about 4 and about 10, or in some examples the pH may be about 7. Suitable bases for adjusting the pH of the peroxymonosulfate solution include alkali metal and alkaline earth metal carbonates and bicarbonates such as sodium bicarbonate, potassium carbonate, and the like. In some examples, the peroxymonosulfate solution may include other ingredients that may function as processing aids, wetting aids, and the like. For example, the peroxymonosulfate solution may include an organic solvent, a surfactant, and / or a phase transfer reagent. Suitable organic solvents include water miscible organic solvents such as acetonitrile, alcohols and the like. Suitable surfactants include anionic, cationic and nonionic surfactants. Suitable phase transfer reagents include, for example, organic quaternary ammonium salts such as tetrabutylammonium bromide. In some examples, the surfactant may further function as a phase transfer reagent, for example, a quaternary ammonium surfactant, cetyltrimethylammonium bromide. In some examples, peroxymonosulfate may be provided as a quaternary ammonium salt, such as OXONE® tetrabutylammonium salt.

In one illustrative example, the method includes contacting a first polymer having a carbonyl group with a mixture of water and KHSO ₅ (potassium peroxymonosulfate). After completion, the polymer with pendant dioxirane is recovered and isolated.

  In another aspect, an article comprising a polymer comprising a pendant dioxirane moiety is provided. Such polymers may be as described above for formulas I, II, III and IV. In some embodiments, the article is a fibrous woven substrate such as a filter. Such a filter may be made by making the polymer into a fiber that is subsequently filtered, or the polymer may be expanded into a foam that is subsequently filtered. The polymer may be filtered either before or after the pendant dioxirane moiety is formed on the polymer. For example, a first polymer containing a carbonyl group is filtered. The filter is then contacted with peroxymonosulfate to form a pendant dioxirane moiety on the polymer. Alternatively, a polymer with pendant dioxirane moieties is filtered. In various embodiments, the article is a fluid filter. For example, the fluid filter may be a gas filter or a liquid filter. Examples of the gas filter include, but are not limited to, an air filter. The filter may be constructed in the same way that household air filters and HEPA filters are constructed.

  For example, a non-woven fibrous substrate such as a filter may be manufactured using blended fibers to create an air permeable substrate. Randomly stacked fiber mats may be produced by commercially available nonwoven manufacturing equipment according to the method indicated by the manufacturer. For example, a suitable device may be RANDO-WEBBER® (Currator Corporation, Rochester, NY).

  Once formed, the fibrous base material having polymer fibers containing pendant carbonyl groups may be contacted with a mixture of water and peroxymonosulfate as described above. The nonwoven fibrous substrate that allows air to pass through may be formed in a conventional manner using non-woven fabric manufacturing equipment. This substrate may be contacted with a peroxymonosulfate solution, for example, by spraying, dipping, etc., in order to obtain the dioxirane groups formed in the polymer from the pendant carbonyl groups. The spent peroxymonosulfate solution may be recovered for reuse and recycling.

  Fibrous substrates produced by such machines may include binders, adhesives, stiffeners and flame retardants, which may be applied after treatment with peroxymonosulfate solution. The filtration characteristics of the fibrous base material may depend on the fiber size, the thickness of the fibrous base material and the type of binder used in the production.

  In a further aspect, a method of gas purification is provided that includes passing a gas through a filter, the filter comprising a polymer comprising a pendant dioxirane moiety, and the gas comprising a biological or chemical contaminant. In another aspect, a method of liquid purification comprising passing a liquid through a filter is provided, the filter comprising a polymer comprising a pendant dioxirane moiety, and the liquid comprising a biological contaminant or a chemical contaminant.

  In some embodiments, the method of gas purification further comprises passing the gas through a filter, wherein the gas includes biological or chemical contaminants. As the gas is passed through the filter, the dioxirane moiety oxidizes the contaminant, resulting in the dioxirane moiety being reduced to a carbonyl or ketone group. The filter may serve to trap oxidized contaminants, or pass oxidized and inactivated contaminants, and the filter simply increases the surface area for the reaction between the polymer and the contaminants But you can. The method may further comprise regenerating the dioxirane after reacting with the contaminant by reacting the ketone group with an effective amount of peroxymonosulfate.

  In another aspect, a method is provided that includes providing a filter comprising a polymer comprising a ketone moiety and converting the ketone moiety to a dioxirane moiety by reacting the polymer with peroxymonosulfate.

  The technology thus generally described will be more readily understood by reference to the following examples. The following examples are provided as examples and are not intended to limit the present technology.

General procedure A: A mixture of water (1 L), sodium hydrogen carbonate (2 M) and 2 KHSO ₅ .KHSO ₄ .K ₂ SO ₄ (2 M with respect to KHSO ₅ ) is continuously passed through the polymer stirrer (100 g) for 1 hour. . The solution is removed by filtration using a Buchner funnel, then washed twice with 50 mL portions of water and then aspirated to remove most of the water. The resulting polymer is then further dried by lyophilization.

  Preparation of a representative polyalkylene terephthalate containing a pendant dioxirane moiety. Polyalkylene terephthalates may be prepared from 1,4-butanediol and terephthaloyl chloride according to known methods, or may be obtained commercially such as from BASF (sold as ULTRADUR). At least one of the carbonyl groups of the polyalkylene terephthalate is oxidized by the general procedure A. Such a process is shown in Scheme 1. Here it should be understood that although both carbonyl groups are converted to dioxirante, only one group may be converted and not all monomer units in the polymer need be converted. is there.

  Preparation of representative poly (methyl) acrylates containing pendant dioxirane moieties according to Scheme 2. The poly (methyl) acrylate may be prepared from methyl acrylate by known methods or may be obtained commercially. The poly (methyl) acrylate is oxidized by the general procedure A. It should be noted that not all monomer units of the polymer need contain dioxirane moieties.

  Preparation of polylactate containing pendant dioxirane moieties according to Scheme 3. An exemplary polylactate, polylactic acid, may be prepared by known methods or may be obtained commercially. Polylactic acid is oxidized by basic procedure A.

  Preparation of polycarbonate containing pendant dioxirane moieties. An exemplary polycarbonate, poly (bisphenol A carbonate), may be prepared by known methods and may be obtained commercially. Poly (bisphenol A carbonate) is oxidized by basic procedure A. Such a process is shown in Scheme 4. Here, it is to be understood that although both carbonyl groups are converted to dioxylants, only one group may be converted and not all monomer units in the polymer need be converted.

  Preparation of polysaccharides containing pendant dioxirane moieties. An exemplary polysaccharide, chitin, is obtained by known methods or obtained commercially. Chitin is oxidized by basic procedure A. Such a process is shown in Scheme 5. Here, it is to be understood that although both carbonyl groups are converted to dioxylants, only one group may be converted and not all monomer units in the polymer need be converted.

  Preparation of polyacetates containing pendant dioxirane moieties according to Scheme 6. Polyvinyl acetate is obtained by known methods or obtained commercially. Polyvinyl acetate is oxidized by basic procedure A.

  Preparation of polystyrene maleic anhydride containing pendant dioxirane moieties. Polystyrene maleic anhydride is easily obtained by known methods or obtained commercially. Polystyrene maleic anhydride is oxidized according to General Procedure A. Such a process is shown in Scheme 7. Here, it is to be understood that although both carbonyl groups are converted to dioxylants, only one group may be converted and not all monomer units in the polymer need be converted.

  Preparation of polyurethane containing pendant dioxirane moieties. Poly (4,4'-diphenylmethane diisocyanate 1,2-ethanediol), exemplary polyurethanes and related fibers are described in Heiss, H. et al. L. Et al., Ind. Eng. Chem. 46, 1498-1503 (1954) and U.S. Pat. Nos. 5,000,899 and 6,533,975 and their references. Poly (4,4'-diphenylmethane diisocyanate 1,2-ethanediol) is oxidized according to General Procedure A. Such a process is shown in Scheme 8. Here, it is to be understood that although both carbonyl groups are converted to dioxylants, only one group may be converted and not all monomer units in the polymer need be converted.

  Preparation of modified polyamides containing pendant dioxirane moieties and quaternary amines according to Scheme 9. Poly (caprolactam) (“nylon 6”) is prepared by known methods or obtained commercially. Poly (caprolactam) was fully methylated by adapting published methods [Org. Synth. Coll, 5, 315 (1973) and references thereof], forming an exemplary polyamide.

Preparation of modified polyacrylamide containing pendant dioxirane moieties according to Scheme 10. Polyacrylamide with a molecular weight range of 5,000,000 to 6,000,000 is obtained by known methods and from commercial sources such as Sigma-Aldrich and Acros Organics. Polyacrylamide was fully methylated by adapting published methods [Org. Synth. Coll, 5, 315 (1973) and references thereof], forming an exemplary polyacrylamide. 100 g of denatured polyacrylamide was then added to a mixture of water (1 L), sodium bicarbonate (2M) and 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ (2M w / r KHSO ₅ ) and 1 with a magnetic stir bar. Stir mechanically for hours. The polymer is then purified by dialysis against distilled water using a dialysis membrane (fraction molecular weight = 1000). Lyophilization gives a modified polyacrylamide containing pendant dioxirane moieties.

Preparation of modified polyacrylamide containing pendant dioxirane moieties according to Scheme 11. An exemplary polyacrylamide, polydimethylacrylamide, is described by Isaure, F .; Et al., React. Funct. Polym. 66, 65-79 (2006). Polydimethylacrylamide is then fully methylated by adapting to published methods [Org. Synth. Coll, 5, 315 (1973) and references]. 100 g of methylated polydimethylacrylamide is then added to a mixture of water (1 L), sodium bicarbonate (2M) and 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ (2M w / r KHSO ₅ )) and magnetically stirred. Stir mechanically with a child for 1 hour. The polymer is then purified by dialysis against distilled water using a dialysis membrane (fraction molecular weight = 1000). Lyophilization gives a modified polyacrylamide containing pendant dioxirane moieties.

  Preparation of poly (methyl) methacrylate containing pendant dioxirane moieties according to Scheme 12. An exemplary methacrylate polymer, poly (methyl) methacrylate, is obtained by known methods and commercial sources such as Sigma-Aldrich. Poly (methyl) methacrylate is oxidized by the general procedure A.

  Preparation of an aramid containing a pendant dioxirane moiety. An exemplary aramid, polyparaphenylene terephthalamide, is obtained by known methods such as the combination of para-phenylenediamine and terephthaloyl dichloride as well as by commercial sources such as DuPont (sold as KEVLAR). Polyparaphenylene terephthalamide is oxidized by basic procedure A. Such a process is shown in Scheme 13. Here, it is to be understood that although both carbonyl groups are converted to dioxylants, only one group may be converted and not all monomer units in the polymer need be converted.

  Preparation of polyurea containing pendant dioxirane moieties. Spandex is obtained by known methods and from commercial sources such as Invista. An exemplary polyurea, spandex, is oxidized according to General Procedure A. Such a process is shown in Scheme 14. Here, it is to be understood that although both carbonyl groups are converted to dioxylants, only one group may be converted and not all monomer units in the polymer need be converted.

Preparation of modified polyurea containing pendant dioxirane moieties. Spandex was fully methylated by adapting published methods [Org. Synth. Coll, Vol. 5, 315 (1973) and references thereof], an exemplary modified polyurea is formed. 100 g of methylated spandex is then added to a mixture of water (1 L), sodium bicarbonate (2M) and 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ (2M w / r KHSO ₅ )) with a magnetic stir bar Stir mechanically for 1 hour. The polymer is then purified by dialysis against distilled water using a dialysis membrane (fraction molecular weight = 1000). Freeze drying gives a modified spandex containing pendant dioxirane moieties. Such a process is shown in Scheme 15. Here, it is to be understood that although both carbonyl groups are converted to dioxylants, only one group may be converted and not all monomer units in the polymer need be converted.

  Preparation of a polymer containing a perfluoro-stabilized pendant dioxirane moiety according to Scheme 16. An exemplary polymer having pendant perfluoro groups, 1,1,1-trifluoro-3,3,4-trimethylpent-4-en-2-one, is prepared according to published methods [Nenajdenko, V .; G. Tetrahedron 50, 11023-11038 (1994)]. 1,1,1-trifluoro-3,3,4-trimethylpent-4-en-2-one is polymerized by adapting to published methods [Zhang, J. et al. Et al., Macromolecules 35, 8869-77 (2002); Monieau, C. et al. Et al., Macromolecules 32, 8277-82 (1999); Gilmer, T .; C. Et al. Polym. Sci. Pol. Chem. 34, 1025-37 (1996) and references]. Poly (1,1,1-trifluoro-3,3,4-trimethylpent-4-en-2-one) is oxidized according to General Procedure A.

  Preparation of a branched backbone polymer containing a perfluoro-stabilized pendant dioxirane moiety according to Scheme 17. An exemplary branched polymer, 4-ethoxy-1,1,1-trifluorobut-3-en-2-one, is obtained by known methods and is commercially available from Sigma-Aldrich. 4-Ethoxy-1,1,1-trifluorobut-3-en-2-one is polymerized by adapting to published methods [Zhang, J. et al. Et al., Macromolecules 35, 8869-77 (2002); Monieau, C. et al. Et al., Macromolecules 32, 8277-82 (1999); Gilmer, T .; C. Et al. Polym. Sci. Pol. Chem. 34, 1025-37 (1996) and references]. Poly (4-ethoxy-1,1,1-trifluorobut-3-en-2-one) is oxidized according to General Procedure A.

  Preparation of poly (methyl-2-keto-3-butenoate) containing pendant dioxirane moieties according to Scheme 18. Methyl-2-keto-3-butenoate is prepared from commercially available 2-keto-3-butenoic acid by adapting to published methods [Org. Synth. Coll, 3, 610 (1995) and references]. Methyl-2-keto-3-butenoate is polymerized by adapting to published methods [Zhang, J. et al. Et al., Macromolecules 35, 8869-77 (2002); Monieau, C. et al. Et al., Macromolecules 32, 8277-82 (1999); Gilmer, T .; C. Et al. Polym. Sci. Pol. Chem. 34, 1025-37 (1996) and references]. Poly (methyl-2-keto-3-butenoate) is oxidized according to General Procedure A.

  Preparation of poly (methyl-2-keto-4-pentenoate) containing pendant dioxirane moieties according to Scheme 19. Methyl-2-keto-4-pentenoate is prepared from commercially available 2-keto-4-pentenoic acid by adapting to published methods [Org. Synth. Coll, 3, 610 (1995) and references]. Methyl-2-keto-4-pentenoate is polymerized by adapting to published methods [Zhang, J. et al. Et al., Macromolecules 35, 8869-77 (2002); Monieau, C. et al. Et al., Macromolecules 32, 8277-82 (1999); Gilmer, T .; C. Et al. Polym. Sci. Pol. Chem. 34, 1025-37 (1996) and references]. Poly (methyl-2-keto-4-pentenoate) is oxidized according to General Procedure A.

  Filtration of liquids with polymers. Place a sterile glass wool stopper at the bottom of the glass column. The glass column is then filled with 100 g dioxirane containing the poly (methyl-2-keto-3-pentenoate) of Example 18. Thereafter, 300 mL of water containing biological contaminants is gently placed into the column. The water is then transferred through the polymer to the receiving flask. Use of the polymer as a filter oxidizes biological contaminants in the water. The filter may further capture oxidized contaminants or the oxidized biological contaminants remain in the water, but its activity is substantially reduced or eliminated as a result of oxidation.

Regeneration of liquid filter. Make a solution of water (1 L), sodium bicarbonate (2 M) and 2 KHSO ₅ .KHSO ₄ .K ₂ SO ₄ (2 M for KHSO ₅ ) (“peroxymonosulfate solution”). After filtration, 300 mL of peroxymonosulfate solution is added to the liquid filter of Example 20. The solution is then transferred through the polymer to the receiving flask to regenerate the dioxirane moiety and help remove degraded contaminants. This may be repeated two more times with a new peroxymonosulfate solution. The liquid filter may then be flushed twice with 100 mL portions of distilled water to remove any remaining salt from the regeneration.

  Air filter production. The polylactic acid containing the pendant dioxirane portion of Example 3 is pressed into a porous sheet. The sheet is then pleated and joined to the steel screen by glueing around the edges of the steel screen.

  Production of air filter using two polymers. The polylactic acid containing the pendant dioxirane moiety of Example 3 and the poly (methyl-2-keto-4-pentenoate) containing the pendant dioxirane moiety of Example 19 are both pressed into a porous sheet. The sheet is then pleated and joined to the steel screen by glueing around the edges of the steel screen.

  Use of the air filter of Example 23. The air filter of Example 23 is placed in the filter holder of a domestic HVAC system. Switch on the HVAC system and operate according to its design. The use of filters in the HVAC system removes biological and chemical contaminants from home air.

  Recycling of the air filter of Example 24. The dioxirane moiety on the polymer filter may be regenerated after the dioxirane moiety on the polymer filter is substantially reduced or after a predetermined period of time. The filter may be sprayed with or dipped in a water-like peroxymonosulfate solution. This solution contains potassium peroxymonosulfate at a concentration of 25 millimolar (OXONE®, DuPont, Wilmington, DE); sodium bicarbonate (Sigma-Aldrich, St. Louis, MO) to adjust the pH to about 7 and A concentration of about 1 mmol of cetyltrimethylammonium bromide (Sigma-Aldrich, St. Louis, MO) may be included. To “recharge” or “recycle” the filter, after spraying or soaking the filter, the carbonyl groups on the polymer are converted to pendant dioxirane moieties. After spraying or immersing the filter in the filter, the filter may be rinsed with distilled water.

Equivalent Forms Although specific embodiments have been shown and described, changes and modifications may be made thereto by ordinary skill in the art without departing from the present technology in its broader aspects as defined in the appended claims. It should be understood that this may be done.

  The embodiments described herein by way of illustration are suitably implemented in the absence of any one or more elements, one or more limitations not specifically disclosed herein. Also good. Thus, for example, the terms “comprising”, “including”, “containing” and the like are interpreted in an expanded manner and are not limited. Moreover, the terms and expressions used herein are used as terms of description rather than limitation, and the use of such terms and expressions may include any equivalent form or feature of the features shown and described. It is recognized that some are not intended to be excluded, and that various modifications are possible within the scope of the claimed technology. Furthermore, the phrase “consisting essentially of” means that the elements specifically listed and any additional elements that do not substantially affect the basic novel characteristics of the claimed technology Is understood to include. The phrase “consisting of” excludes any element not specified.

  This disclosure is not intended to be limited with respect to the specific embodiments described in this application, but is intended to illustrate various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. In addition to those listed herein, functionally equivalent compositions, devices, and methods within the scope of this disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is limited only by the terms of the appended claims, with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, compositions or biological systems, which can of course vary. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

  Furthermore, if a feature or aspect of the present disclosure is described by a Markush group, those skilled in the art will recognize that the present disclosure is thereby described in terms of any individual member or member subgroup of the Markush group. Will.

  As will be appreciated by those skilled in the art, for any and all purposes, particularly with respect to providing the specification, any range disclosed herein may be any and all possibilities. Also included are subranges and combinations of subranges. Any given range is well-recognized and readily recognized as allowing the decomposition of the same range into at least 2 equal parts, 3 equal parts, 4 equal parts, 5 equal parts, 10 equal parts, etc. Can be done. By way of non-limiting example, each range described herein can be easily decomposed into a lower third, middle third, upper third, and the like. As will also be appreciated by those skilled in the art, all terms such as “maximum”, “at least”, “greater”, “less than”, etc. include the recited numbers, followed by A range that can be decomposed into ranges. Similarly, the phrase “at least about” any value, such as weight percent, includes at least that value and approximately that value. For example, “at least about 1% by weight” means “at least 1% by weight or about 1% by weight”. Finally, as will be appreciated by those skilled in the art, each range includes individual members.

  Other embodiments are in the claims.

Claims (7)

A polymer comprising at least one pendant dioxirane moiety,

Is a polymer . A gas purification method comprising passing gas through a filter, wherein the filter comprises a polymer comprising a pendant dioxirane moiety according to claim 1 . The method of claim 2 , wherein the gas comprises a biological contaminant or a chemical contaminant. 4. The method of claim 2 or 3 , further comprising recycling the filter comprising exposing the filter to a solution comprising peroxymonosulfate. A method of liquid purification comprising passing a liquid through a filter, wherein the filter comprises a polymer comprising a pendant dioxirane moiety according to claim 1 . 6. The method of claim 5 , wherein the liquid comprises biological contaminants or chemical contaminants. 7. The method of claim 5 or 6 , further comprising recycling the filter comprising exposing the filter to a solution comprising peroxymonosulfate.