WO2022051762A2 - Non-leaching waterborne virucidal/bactericidal coating - Google Patents

Non-leaching waterborne virucidal/bactericidal coating Download PDF

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Publication number
WO2022051762A2
WO2022051762A2 PCT/US2021/071352 US2021071352W WO2022051762A2 WO 2022051762 A2 WO2022051762 A2 WO 2022051762A2 US 2021071352 W US2021071352 W US 2021071352W WO 2022051762 A2 WO2022051762 A2 WO 2022051762A2
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Prior art keywords
compound
agent
substituted
group
biocidal
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PCT/US2021/071352
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French (fr)
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WO2022051762A3 (en
Inventor
Seamus Curran
Kang-Shyang Liao
Alexander J. WANG
Surendra MAHARJAN
Eileen MELLON
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Curran Biotech Inc.
University Of Houston
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Publication of WO2022051762A2 publication Critical patent/WO2022051762A2/en
Publication of WO2022051762A3 publication Critical patent/WO2022051762A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic

Definitions

  • This disclosure relates to water-based virucidal/bactericidal coating compositions. More specifically, portions of this disclosure relate to non-leaching, biocompatible, non-cytotoxic, breathable, water-based virucidal/bactericidal coating compositions that also renders the coated surface permanently hydrophobic, and uses thereof, including but not limited to air-filtration media.
  • Substrates including fabrics and filters therefore not only require a liquid repellent, as the medium by which many infectious agent(s)/viruses travel is largely aqueous, but also an active compound(s) to deactivate/lyse any infectious agent that comes into contact with the substrate surface before it becomes a transmissible contagion. While such protective measures are critical for decreasing transmission of infectious agents/contagions, current chemical treatments do not provide such a solution.
  • the coating can either penetrate porous substrates, be layered on tarpaulin-type materials, and/or be bonded to fibers such as those used in fabrics/textiles and imparts surface(s) of the coated substrate with active compound(s) that cause damage to the capsid/outer envelope protein layer, spike protein, or a process that could eventually lead to forms of viral/bacterial de-activation or lysis.
  • hydrophobic water-based coating composition(s) can be used to treat substrates to inhibit viral/bacterial contamination, such as transmittal from human to human, animal to human (e.g., zoonotic diseases/zoonosis), human to animal, and/or via surface contact and/or deposition onto surfaces, fabrics, and other porous substrates that are shared to any extent (e.g., various substrates that may come into contact with more than one human/animal).
  • viral/bacterial contamination such as transmittal from human to human, animal to human (e.g., zoonotic diseases/zoonosis), human to animal, and/or via surface contact and/or deposition onto surfaces, fabrics, and other porous substrates that are shared to any extent (e.g., various substrates that may come into contact with more than one human/animal).
  • a surface that is hydrophilic in nature in particular when it comes to coating face masks or filters used in, for example, medical treatments and HVAC systems.
  • human infectious agent(s)/contagion(s) typically transmit and propagate either directly via contact with static/airbome infectious respiratory droplets, bodily fluids, or excrement, as well as indirectly via contact with fomites, vectors, or contaminated commonly touched objects/surfaces in the environment.
  • transmission of infectious agent(s)/contagion(s) can depend on droplet size transmitted through regular respiration, coughing, or sneezing.
  • droplet formation can occur in a number of ways, including shear stress and dynamic compression along the mucus-air interface, which dislodges mucus and results in the formation of small droplets.
  • Respiratory droplet formation characteristics are dependent mainly on place of origin. Large droplet formation is typically a consequence of oral cavity expulsion (-50- 100 pm) whereas smaller droplets are formed when they originate from the bronchioles ( ⁇ 0.6 - 16 pm), although the presence of viral infections can alter the droplet size.
  • the fundamental principle of using filters to capture respiratory droplets or particles containing infectious agent(s)/contagion(s) is based on the fiber weave of the filter and its interconnectedness and thickness, the incoming flow of air and particulates, and the aerosol properties of the droplets or particles.
  • the pathways used by particulates inside the filter weave and through the filter fibers are based on flow properties including inertial impaction, interception, and diffusion mechanisms. Large particles ranging from 60-100 pm fall to the ground due to gravity after 2 meters, which may take only -10 seconds, although will be readily stopped at a filter if expelled towards the filters. These large droplets are carried further away when they are expelled at high velocity, such as with coughs and sneezes.
  • the water-based coating composition(s) disclosed herein may be designed to exhibit an affinity towards infectious virions with a hydrophilic surface chemistry and facilitate spreading and absorption of the infectious respiratory droplets and/or respiratory droplet nuclei in which they exist outside the host to maximize the surface area and optimize interfacial interactions between the infectious virions/microbes and active compound(s), acting both as a filter and virucide/bactericide.
  • the coatings described herein may likewise be used as a filtration system for the blood stream.
  • Certain infectious virions are attracted to the oxygen in blood and as such can successfully exist even outside the human respiratory system.
  • the treated membranes act as a mechanism to clean blood of the infectious species. Samples of these filters can then be analyzed to determine the presence of the infectious virions/microbes using optical techniques where distinctive optical fingerprinting can be carried out, thereby determining the presence and relative concentration of the infectious virions/microbes .
  • Embodiments of this disclosure include non-leaching, biocompatible, non-cytotoxic, breathable, water-based virucidal/bactericidal coating compositions that also render the coated surface permanently hydrophobic, and uses thereof, including but not limited to air-filtration media.
  • Such coating compositions include one or more active compounds, graft polymer backbone agents, and emulsifying agents.
  • the active compound(s) in the coating compositions may potentially include derivatives of quaternary ammonium/phosphonium compounds, tertiary sulfonium compounds, polyionic compounds, metal salts, metal nanoparticles, metal-oxide nanoparticles, reactive oxygen-generating species, N-halamines, and/or bio macromolecules acting as immobilized virucidal/bactericidal agents.
  • the functionality of the active compound(s) may electively include virucidal/bactericidal properties but are not restricted exclusively to such biocidal activity.
  • the virucidal/bactericidal coating compositions are water-borne and may include one or more solvents/co- solvents.
  • the virucidal/bactericidal coating compositions described herein may potentially include one or more tagging agents.
  • the tagging agent(s) may potentially include but not limited to sulphonated multi-block copolymers and silane-capped copper nanoclusters.
  • tagging agents the molecules or changes to their structures are detectible by advanced and/or combinatory spectroscopy techniques such as infrared, fluorescence tagging, and Raman spectroscopies as a diagnostic tool to detect the presence of infectious species- specific virions and/or microbes.
  • water-based or “water-borne” as used herein refer to aqueous coating compositions with a water concentration greater than or equal to 25% of the net coating composition by volume.
  • hydrophobic refers to a property of a material where the material impedes the wetting and/or absorption of water or water-based liquids. In general, a material lacking affinity to water may be described as displaying “hydrophobicity”.
  • hydrophilic refers to a property of a material where the material exhibits the tendency to mix with, dissolve in, or attract the wetting and/or absorption of water or waterbased liquids. In general, a material exhibiting affinity to water may be described as displaying “hydrophilicity”.
  • viral refers to the ability of a material to deactivate, inhibit, and/or lyse viruses; inhibit/thwart transmission of infectious agents/contagions, or minimize host-cell damage, transformation, growth, nucleation, twinning, reproduction of the infectious agent/pathogen/contagion. In some aspects, this also encompasses the ability of a material to resist the attack or layering (settling on the surface) of infectious agents/contagions like enveloped viruses, including SARS-CoV-2, Influenza A viruses, and Ebola viruses.
  • bacteriaicidal refers to the ability of a material to destroy bacteria; resist entrance of bacteria, or suppress bacterial growth or reproduction. More specifically, it also refers to the ability of a material to resist the attack of bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica, and Pseudomonas aeruginosa.
  • antiimicrobial is a term used to describe any applicable surface or material that has been coated, sealed, or treated to impart the ability to kill microorganisms (i.e.
  • microbicidal and substantially inhibit their growth.
  • the United States Environmental Protection Agency (EPA) states this use as to disinfect, sanitize, reduce, or mitigate growth or development of microbiological organisms.
  • the application is to protect against bacteria and viruses.
  • one may also define and differentiate the microbe(s) being killed such as, for example, SARS-CoV-2, then term would be specifically antiviral.
  • a surface or material that exhibits limited antimicrobial behavior or properties is said to be “microbial resistant”. Specifically, the material may be seen to inhibit or impede the rate at which microbes proliferate on or attach to a surface.
  • anti-COVID and “COVID-resistance” are defined as a property exhibited by specifically-designed functional coatings or functionalized/chemically-modified surfaces that either inhibit or aid in the removal of a select assortment of human coronaviruses (COVIDs).
  • C OVID -contaminated refers to the undesired settlement, anchoring, and/or colonization of the aforementioned COVID agents on the surfaces or internal components of COVID agents adhered to fabrics used in personal protective equipment in hospitals or care facilities.
  • breathable refers to a material having a water vapor transmission rate of at least about 300 grams/m 2 /24 hours.
  • the coatings discussed herein can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the coatings are their abilities to provide antibacterial, antiviral, or antimicrobial properties and water repellency for a substrate, which inhibits leaching of the active compound from the substrate.
  • FIG. 1 illustrates a method of forming a substrate coating according to some embodiments of the disclosure.
  • FIG. 2 illustrates a method of treating a substrate with a coating according to some embodiments of the disclosure.
  • FIG. 3 is a schematic of a filter for capturing SARS-CoV-2 using a coating according to one of the embodiments of this disclosure.
  • FIG. 4A is a graph of relative fluorescence curves after 45 amplification/denaturation polymerase chain-reaction cycles (right) for pristine/untreated MERV 8 and MERV 13 filters against a MVTR-A1 -treated MERV 8 filter according to one of the embodiments of this disclosure.
  • FIG. 4B is a graph of relative fluorescence values after 45 amplification/denaturation polymerase chain-reaction cycles (right) for pristine/untreated MERV 8 and MERV 13 filters against a MVTR-A1 -treated MERV 8 filter according to one of the embodiments of this disclosure.
  • FIG. 5 provides cycle quantification values of untreated MERV 8, 11, 13, and 14 filters compared against a MVTR-A1 -treated MERV 8 filter after 45 amplification/denaturation cycles according to one of the embodiments of this disclosure.
  • FIG. 6 shows theoretical filter efficiency mapped against actual and equivalent cycle qualification values for a MVTR-A1 -treated MERV 8 filter and MERV 6-16 filters according to one of the embodiments of this disclosure, where experimental data corresponding to data points was obtained for untreated MERV 8-14 filters.
  • FIG. 7 provides cycle quantification values versus time according to one of the embodiments of this disclosure, where swabs of “captured” virus were taken of the front face of a filter.
  • FIG. 8 is a diagram showing fractional efficiency against particle diameter according to one of the embodiments of this disclosure.
  • FIG. 9A provides averaged optical-photothermal infrared (O-PTIR) spectra data for pristine/untreated cotton and MVTR-A1 -treated cotton according to one of the embodiments of this disclosure.
  • O-PTIR optical-photothermal infrared
  • FIG. 9B provides averaged Raman spectra data for pristine/untreated cotton and MVTR- Al -treated cotton according to one of the embodiments of this disclosure.
  • Embodiments of the disclosure may be used in non-leaching, biocompatible, non- cytotoxic, breathable, water-based virucidal/bactericidal coating/carrier compositions and methods of using/applying the composition(s) to treat porous or nonporous substrates to provide protection against infectious agent(s)/contagion(s)/pathogen(s) that cause infectious diseases, such as COVID- 19, via mechanisms-of-action that include but are not limited to deactivation, inhibition, termination, and/or lysis of the infectious agent(s)/contagion(s)/pathogen(s).
  • the coating composition includes one or more active compounds, graft polymer backbone agents, and emulsifying agents.
  • the active compound(s) in the coating compositions may potentially include derivatives of quaternary ammonium/phosphonium compounds, tertiary sulfonium compounds, polyionic compounds, metal salts, metal nanoparticles, metal-oxide nanoparticles, reactive oxygen-generating species, N-halamines, and/or biomacromolecules acting as immobilized virucidal/bactericidal agents.
  • the virucidal/bactericidal coating compositions are water-borne and may or may not include one or more solvents/co- solvents.
  • the coating composition is either hydrophilic or hydrophobic and is suitable for treating/coating/functionalizing porous/nonporous substrates, including but not limited to functionalization of porous plastics, layering on tarpaulinsubstrates, and coating/functionalizing synthetic/organic fibers such as those used in manufacturing fabrics, textiles, linens, garments, personal protective equipment, masks, respirator masks, and fiber materials used for manufacturing air filters (for heating, ventilation, purification, and air conditioning as well as biological based applications in filters used in systems such as dialysis).
  • Other substrates may also include masonry, concrete, stone, brick, stucco, grout, woodbased products, fences, decks, furniture, and porous ornaments.
  • the changes in the fabrics or treated surfaces due to viral/bacterial presence may also be detected using spectroscopy techniques using either hand-held or bench top instruments.
  • An antibacterial, antiviral, or antimicrobial water-based coating composition is discussed herein that addresses the problems associated with addition of active compound(s), in particular, quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such, to a substrate.
  • active compound(s) in particular, quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such, to a substrate.
  • the premise of the water-based coating composition lies in the ability to functionalize the substrate with a low-dimensional water-based coating composition that includes active compound(s), in addition to coating the surface of the substrate.
  • the active compound(s) can be composition(s) that protect against transmission of infectious diseases from bacteria or viruses, such as quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such.
  • the water-based coating composition can provide protection against transmission of infectious diseases from bacteria/viruses, like disease-causing viruses (e.g., SARS-CoV-2, MERS-CoV, Influenza A, Ebola, and AIDS) and other infectious agents/contagions .
  • the various compounds used for the coating form an effective hydrophobic layer and thus provide resistance against leaching or loss of the active compound(s) from substrates, such as by water through washing, evaporation, or exposure to exterior environments.
  • the water-based coating composition is hydrophobic and is suitable for treating/coating porous substrates, functionalizing porous plastics, layering on tarpaulin, or coating/functionalizing synthetic/organic fibers, such as those used in manufacturing fabric, linens, garments, and masks, fiber materials used for manufacturing air filters (for heating, ventilation, and air conditioning systems (HVAC)), masonry materials, or aquatic structures.
  • HVAC heating, ventilation, and air conditioning systems
  • the water-based coating compositions described herein may be used to enhance the virus-/microorganism-carrier filtration efficiency performance of HVAC air-filters without affecting airflow and may be applied using conventional methods including but not limited to spraying or dipping.
  • the components of the waterbased coating composition act as a carrier for the active compound(s) preventing transmission of infectious diseases, which enables deposition and penetration of the quaternary ammonium/phosphonium compound(s), sulfonium compound(s), or derivative(s) of such on and into substrate(s).
  • the carrier can include a solution of hydrophobic chemical agent(s) in some embodiments.
  • the active compound(s) e.g., quaternary ammonium/phosphonium compound(s), or derivative(s) of such
  • the hydrophobic chemical agent(s) e.g., formation of a covalent bond
  • the hydrophobic chemical agent(s) e.g., formation of a covalent bond
  • the water-based coating composition can also provide an effective, breathable, penetrating, virucidal/bactericidal coating which exhibits broad spectrum virucidal and bactericidal properties via a simple coating process that prevents/reduces premature leaching or loss of active compound(s) to maintain long term inhibition against infectious agents/contagions.
  • Viral/bacterial resistance/inhibition/deactivation may be achieved via the inclusion of one or more species of active compounds, such as quaternary ammonium/phosphonium compound(s) or tertiary sulfonium compound(s) that are either target- specific or more general in the particular mechanism of action by which they inhibit, deactivate, and/or lyse the infectious agent(s)/contagion(s).
  • active compounds such as quaternary ammonium/phosphonium compound(s) or tertiary sulfonium compound(s) that are either target- specific or more general in the particular mechanism of action by which they inhibit, deactivate, and/or lyse the infectious agent(s)/contagion(s).
  • active compounds such as quaternary ammonium/phosphonium compound(s) or tertiary sulfonium compound(s) that are either target- specific or more general in the particular mechanism of action by which they inhibit, deactivate, and/or ly
  • the outer proteins carry out a number of critical steps, which include standard packaging of the viral RNA as well as helping the viral RNA link up with its replicating enzymes.
  • the coating inhibits the reproducibility and survivability of infectious viral agents/contagions on the protected surface/substrate.
  • Embodiments relate to water-based coating compositions and methods for making water-based coating compositions for substrates.
  • a hydrophobic waterbased coating composition is capable of inhibiting/reducing the transmission of infectious diseases in the environment.
  • the hydrophobic water-based coating composition can include water, at least one active compound (e.g., quaternary ammonium/phosphonium compounds, tertiary sulfonium compounds, polyionic compounds, metal salts, metal nanoparticles, metal-oxide nanoparticles, reactive oxygen-generating species, N-halamines, and/or biomacromolecules or derivative(s) of such acting as immobilized virucidal/bactericidal agents), at least one graft polymer backbone agent, and at least one non-ionic emulsifying agent.
  • the composition may also include one or more base compounds, co-solvents, bonding agents, plasticizers and other functional additives.
  • the water-based coating composition is capable of depositing the active compound(s) not only to the surfaces of the substrate, but also soaking, penetrating, or permeating into internal portions of the substrate (e.g., such that the active compound(s) renders the entirety of the substrate active, not merely the surface).
  • the active compound(s) of the water-based coating composition are quaternary ammonium/phosphonium compound(s) or derivative(s) of such that can include a quaternary ammonium/phosphonium cation, which includes a positively charged polyatomic ion with the structure
  • Q is either a nitrogen or phosphorous atom and R is an aryl, alkyl, phenyl, benzyl, allyl, alkenyl, or alkynyl group, and the ammonium/phosphonium cations are permanently charged regardless of the pH environment in which they exist.
  • silyl ether, alkoxy silyl, hydroxysilyl, and silyl halide quaternary ammonium/phosphonium silanes can have a general formula of: where Q is either a nitrogen atom or phosphorous atom, R 1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group; R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group,
  • silyl ether, trialkoxysilyl, trihydroxysilyl quaternary ammonium/phosphonium compounds can have a general formula of: where Q is either a nitrogen atom or phosphorous atom, R 1 is a hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an un
  • quaternary ammonium organosilanes used may include but are not limited to: DIMETHYLOCTADECYL[(3-TRIHYDROXYSILYL)PROPYL] AMMONIUM
  • TRIMETHOXYSILYL PROPYL] AMMONIUM CHLORIDE (CAS#: 27668-52-6), 3- (TRIMETHOXYSILYL)PROPYL-N,N,N-TRIMETHYLAMMONIUM CHLORIDE (CAS#: 35141-36-7), TETRADECYLDIMETHYL(3-TRIMETHOXYSILYLPROPYL)AMMONIUM CHLORIDE, N,N-DIDECYL-N-METHYL-N-(3-TRIMETHOXYSILYLPROPYL)
  • TRIMETHOXYSILYLPROPYL AMMONIUM CHLORIDE (CAS#: 41591-87-1) and 4- (TRIMETHOXYSILYLETHYL)BENZYLTRIMETHYL AMMONIUM CHLORIDE.
  • the quaternary phosphonium organosilanes described and utilized may be formed via reaction of a nucleophilic phosphine-functional compound (e.g., TRIPHENYLPHOSPHINE (CAS#: 603-35-0), DICYCLOHEXYL[2,4,6-TRIS(1- METHYLETHYL)PHENYL]PHOSPHINE (CAS#: 303111-96-9)) with an electrophilic halogenfunctional organosilane (e.g., 3-CHLOROPROPYLTRIMETHOXYSILANE (CAS#: 2530-87-2), ((CHLOROMETHYL) PHENYLETHYL) TRIMETHOXYSILANE (CAS#: 68128-25-6)) via SN2-type nucleophilic substitution to form a quaternary phosphonium organosilane with a cationic phosphonium group stabilized with the anionic halogen leaving group from the hal
  • the quaternary phosphonium organosilanes described and utilized may be formed via reaction of a nucleophilic phosphine-functional organosilane (e.g. 2-(DIPHENYLPHOSPHINO) ETHYLTRIETHXOYSILANE (CAS#: 18586-39-5), 3- (DIPHENYLPHOSPHINO) PROPYLTRIETHOXYSILANE (CAS#: 52090-23-0) VINYL (DIPHENYLPHOSPHINOETHYL)DIMETHYLSILANE (CAS#: 76734-22-0)), with an electrophilic alkyl halide (e.g., 1 -CHLOROOCTADECANE (CAS#: 3386-33-2), 1- CHLOROHEXADECANE (CAS#: 4860-03-1), CHLOROMETHANE (CAS#: 74-87-3)) to form a quaternary phosphonium organosilane with a nucleophilic phosphine-
  • the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents.
  • the concentration of the quaternary ammonium/phosphonium organosilanes in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%,
  • 0.1500% 0.1500%, 0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%,
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • concentration of the active compound(s) in the water-based coating composition is between 0.1 and 10 vol. %.
  • the active compound(s) of the water-based coating composition are tertiary sulfonium compound(s) or derivative(s) of such that can include a tertiary sulfonium cation, which includes a positively charged polyatomic ion with the structure
  • R is an aryl, alkyl, phenyl, benzyl, allyl, alkenyl, or alkynyl group, and the sulfonium cations are permanently charged regardless of the pH environment in which they exist.
  • silyl ether, alkoxy silyl, hydroxysilyl, and silyl halide tertiary sulfonium compounds can have a general formula of: where R 1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group; R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted ally
  • silyl ether, trialkoxysilyl, and trihydroxysilyl tertiary sulfonium compounds can have a general formula of: where R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and
  • An example of a commercially available tertiary sulfonium organosilane described and used may include but is not limited to: S-(TRIMETHOXYSILYLPROPYL)ISOTHIOURONIUM CHLORIDE (CAS#: 84682-36-0).
  • the tertiary sulfonium organosilanes described and utilized may be formed via reaction of a nucleophilic thioether/sulfide-functional compound (e.g., POLY(1,4-PHENYLENE SULFIDE) (CAS#: 25212-74-2)) with an electrophilic halogenfunctional organosilane (e.g., 3-CHLOROPROPYLTRIMETHOXYSILANE (CAS#: 2530-87-2), ((CHLOROMETHYL) PHENYLETHYL) TRIMETHOXYSILANE (CAS#: 68128-25-6)) via SN2-type nucleophilic substitution to form a tertiary sulfonium organosilane with a cationic sulfonium group stabilized with the anionic halogen leaving group from the halogen-functional organosilane.
  • a nucleophilic thioether/sulfide-functional compound e.g., PO
  • the tertiary sulfonium organosilanes described and utilized may be formed via reaction of a nucleophilic sulfide-functional organosilane (e.g., BIS[m- (2-TRIETHOXYSILYLETHYL)TOLYL]POLYSULFIDE (CAS#: 198087-81-9/85912-75- 0/67873-85-2), BIS [TRIETHOXYSIL YL)PROPYL]TETRASULFIDE (CAS#: 40372-72-3), 3- MERCAPTOPROPYLTRIMETHOXYSILANE (CAS#: 4420-74-0)) with an electrophilic alkyl halide (e.g., 1 -CHLOROOCTADECANE (CAS#: 3386-33-2), 1 -CHLOROHEXADECANE (CAS#: 4860-03-1), CHLOROMETHANE (CAS#: 74-87-3)) to form a tertiary organosilane (e.g
  • the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents.
  • concentration of the tertiary sulfonium organosilanes in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about
  • the percentage can be calculated by weight or volume of the total composition.
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • concentration of the active compound(s) in the water-based coating composition is between 0.1 and 10 vol. %.
  • quaternary ammonium/phosphonium and tertiary sulfonium organosilanes are alkoxy-, hydroxyl-, or halide-functional organosilanes with a quaternary amine/phosphine- functional or sulfonium-functional linear/branched alkyl chain.
  • These compounds are known to exhibit antimicrobial/bactericidal/virucidal properties that can be effectively implemented in biocidal systems, which include but are not limited to microbicides, virucides, bactericides, fungicides, and algaecides.
  • hydrolysable alkoxy, hydroxyl, or halide moieties of a quaternary ammonium/phosphonium or tertiary sulfonium organosilane may undergo condensation reactions with silanol, hydroxyl, or halogen moieties of a polymeric host matrix and/or with other quaternary ammonium/phosphonium and/or tertiary sulfonium organosilane compounds in either the presence or absence of a catalyst.
  • the antimicrobial properties of quaternary ammonium/phosphonium and tertiary sulfonium organosilanes arise from positively charged ammonium/phosphonium/sulfonium moieties that exhibit an affinity for the anionic heads of phospholipids that function as critical bilayer-forming components of most cellular membranes or outer protein envelopes/capsids of infectious agents like viruses.
  • the proximity between such ammonium/phosphonium moieties and the lipid bilayers of cellular membranes is enhanced by quaternary ammonium/phosphonium and tertiary sulfonium silanes with longer alkyl chain moieties that facilitate and amplify weak intermolecular attraction between the two.
  • the active compound(s) of the water-based coating composition are polymers and/or derivatives of polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyethylacrylic acid (PEAA), polypropylacrylic acid (PPAA), polyvinylbenzoic acid (PVBA), or a copolymer of any combination of above monomers (acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid and vinylbenzoic acid), said polymers having an average molecular weight from 25,000 to 1,000,000 Da.
  • PAA polyacrylic acid
  • PMAA polymethacrylic acid
  • PEAA polyethylacrylic acid
  • PPAA polypropylacrylic acid
  • PVBA polyvinylbenzoic acid
  • PVBA polyvinylbenzoic acid
  • the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents.
  • concentration of the polymers in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%,
  • the percentage can be calculated by weight or volume of the total composition.
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • concentration of the active compound(s) in the water-based coating composition is between 0.1 and 10 vol. %.
  • the polymers may exist in full or partially anionic forms with alkali metal counter ions (preferably sodium or potassium).
  • alkali metal counter ions preferably sodium or potassium.
  • PAA and PMAA were found to have antiviral properties in tissue culture and are less cytotoxic. In vitro study showed that PAA and PMAA inhibited the adsorption of the virus to the host cell and suppressed the one-cycle viral synthesis in tissue cultures inoculated with infectious RNA (De Somer et al. J. Virol. 1968, 2, 878-885).
  • the tagging agent(s) of the breathable, waterborne, virucidal/bactericidal coating compositions may include copper nanoclusters capped by a silane, which can be used to determine the presence of the infectious virions.
  • the copper nanoclusters capped by a silane exhibit a chromatic shift in the presence of the virus as associated chelating effects activate the copper under UV irradiation.
  • Such a scheme provides a way to not only disrupt viral transmission but also serves as a means to detect the presence of the virus using fluorescence spectroscopy or confocal fluorescence microscopy techniques.
  • charged multiblock polymers may be used, wherein the midblock is selectively sulfonated, and therefore hydrophilic. Midblock sulfonation is attributed to a dramatic reduction in surface pH level, and this leads to gram negative results when bacteria accumulate in the lungs due to COVID-19-related infections.
  • the polymers can be used as markers to detect using UV irradiation and fluorescence microscopy the presence of bacteria caused by the presence of COVID-19 and potentially the virus itself.
  • the water-based coating composition for treating the surface of materials may also include graft polymer backbone agent(s).
  • the graft polymer backbone agent(s) may be hydrophobic and may have a general formula of alkoxyalkylsilane
  • [alkoxy] comprises methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or a combination thereof;
  • R 7 comprises a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, or derivatives thereof, and a is an integer from 0 to 20, b is the integer 1, 2, or 3, c is the integer 0, 1, 2, or 3, and d is the integer 1, 2, or 3, provided that the sum of b, c, and d equals 4.
  • the preferred alkoxyalkylsilane species may include, but are not limited to, trimethoxyisobutylsilane, triethoxyisobutylsilane, dimethoxydiisobutylsilane, diethoxydiisobutylsilane, trimethoxy(hexyl)silane, triethoxy(hexyl)silane, tripropoxy(hexyl) silane, triisopropoxy(hexyl) silane, trimethoxy(octyl)silane, triethoxy(octyl)silane, tripropoxy(octyl)silane, triisopropoxy(octyl) silane, trimethoxy(decyl)silane, triethoxy(decyl) silane, tripropoxy(decyl)silane, triisopropoxy(decyl)silane, trimethoxy(decyl)
  • the hydrophobic chemical agent(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents.
  • the concentration of the hydrophobic graft polymer backbone agent(s) having a general formula of alkoxy alkyl silane in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%,
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • concentration of the graft polymer backbone agent(s) in the coating composition is between 0.1 and 15 vol. %.
  • the water-based coating composition for treating the surface of materials may also include graft polymer backbone agent(s).
  • graft polymer backbone agent(s) may comprise at least one functional silicone/siloxane in oligomer/co -oligomer form, polymer/co-polymer form, or a combination thereof having a nonlimiting generalized formula of: with an average molecular weight between 100 to 100,000 Da and an average viscosity between 10 to 20,000 mPa- s, where R a , R b , R c , R d , R e , R f , R g , and R h are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an un
  • X and X’ are an alkoxy group, hydroxyl group, halogen, hydrogen, vinyl group, mercapto/thiol group, amine group, epoxide group, unsubstituted/substituted alkene group, unsubstituted/substituted alkyne group, unsubstituted/substituted allyl group, unsubstituted/substituted alkynyl group, unsubstituted/substituted alkenyl group, an unsubstituted/substituted alkyl group, or a combination thereof, where X and X’ may be the same or dissimilar, z and j are integer values between 1-200,000, where z and j may or may not be equal to one another.
  • Such preferred functional silicone/siloxane species may include but are not limited to, VINYL-TERMINATED DIPHENYLSILOXANE COPOLYMER (CAS#: 68951-96-2), VINYL- TERMINATED POLYDIMETHYLSILOXANES (CAS#: 68083-19-2),
  • DIMETHYLSILOXANE COPOLYMER TRIMETHYLS ILOXY-TERMINATED (CAS#: 68037-59-2), METHYLHYDROSILOXANE-PHENYLMETHYLSILOXANE COPOLYMER,
  • the hydrophobic chemical agent(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents for subsequent reaction(s).
  • the concentration of the graft polymer backbone agent(s) comprising at least one functional silicone/siloxane in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about
  • the percentage can be calculated by weight or volume of the total composition.
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • concentration of the hydrophobic chemical agent(s) in the water-based coating composition is between 0.1 and 15 vol. %.
  • the graft polymer backbone agent(s) may be either hydrophobic/hydrophilic and comprise at least one functional silicone/siloxane in oligomer/co- oligomer form, polymer/co-polymer form, or a combination thereof, in combination with a substituted/unsubstituted alkyl functional silyl ether, halogensilane, or silyl hydride having a nonlimiting generalized formula of: where R a , R b , R c , and R d are each independent hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group
  • Such preferred substituted/unsubstituted alkyl-functional silyl ethers, halogensilanes, and silylhydrides include but are not limited to, trimethoxy(hexyl)silane, triethoxy(hexyl)silane, tripropoxy(hexyl) silane, tri-isopropoxy(hexyl)silane, trimethoxy(octyl)silane, triethoxy(octyl)silane, tripropoxy(octyl) silane, tri-isopropoxy(octyl) silane, trimethoxy(decyl) silane, triethoxy(decyl) silane, tripropoxy (decyl) silane, tri-isopropoxy(decyl)silane, trimethoxy(dodecyl)silane, triethoxy(dodecyl) silane, tripropoxy(dode
  • the hydrophobic chemical agent(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents for subsequent reaction(s).
  • the concentration of the graft polymer backbone agent(s) comprising at least one functional silicone/siloxane in combination with a substituted/unsubstituted alkyl functional silyl ether, halogensilane, or silyl hydride in the waterbased coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%,
  • 0.1500% 0.1500%, 0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%
  • graft polymer backbone agent(s) comprising at least one functional silicone/siloxane in combination with a substituted/unsubstituted alkyl functional silyl ether, halogensilane, or silyl hydride mentioned throughout the specification and claims.
  • the percentage can be calculated by weight or volume of the total composition.
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • concentration of the hydrophobic chemical agent(s) in the water-based coating composition is between 0.1 and 15 vol. %.
  • the water-based coating composition for treating the surface of materials may also include emulsifying agent(s).
  • the emulsifying agent(s) may include one or more nonionic surfactants, including the use of other chemical agents either alone or in conjunction with nonionic surfactants to perform similar tasks as emulsifying agents.
  • the nonionic emulsifying agent comprises at least one, preferably ethoxylated, nonionic amphiphilic compound in monomeric form, oligomeric/co -oligomeric form, polymeric/co- polymeric form, or a combination thereof having nonlimiting generalized formulas: where E is either a hydrocarbon moiety having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted
  • other chemical agents may be nonionic ethoxylated/alkoxylated fatty acids, ethoxylated alcohols, secondary ethoxylated alcohols, ethoxylated amines, alkyl and nonyl-phenol ethoxylates, ethoxylated sorbitan esters, polysorbates, and ethoxylated oils.
  • the preferred nonionic emulsifying agent species may include, but are not limited nor restricted to, 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, ethoxylated tridecyl alcohols, isodecyl alcohol ethoxylates, linear/branched secondary alcohol (C4-C24) ethoxylates, ethoxylated-propoxylated 2-ethyl hexanol, nonylphenoxy poly(ethyleneoxy)ethanol, branched, sorbitan monopalmitate, polyethylene glycol dodecyl ether, di(propylene glycol)monomethyl ether, ethylene diamine tetrakis(ethoxylate-block-propoxylate) tetrol, 2,4,7,9-tetramethyl-5- decyne-4,7-diol ethoxylate, oc-octadecyl- «)-hydroxy-poly(oxy-l)-l
  • the concentration of the emulsifying agent(s) in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%,
  • 0.1500% 0.1500%, 0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%
  • the percentage can be calculated by weight or volume of the total composition.
  • the water-based coating composition for treating the surface of materials may also include solvent(s).
  • the solvent(s) used to disperse all the components to form a homogeneous solution/emulsion may include, but is not limited to, methanol, ethanol, phenoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol acetone, acetonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, di(propylene glycol) methyl ether, 4-chlorobenzotrifluoride, odorless mineral spirits/petroleum distillates or a mixture/combination thereof.
  • the concentration of the solvent(s) in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%,
  • the percentage can be calculated by weight or volume of the total composition.
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • the water-based coating composition may optionally include one or more base compounds, bonding agents, plasticizers, chelating agents, and/or other functional additives.
  • the base compound(s) are a core unit or base of the sol-gel network.
  • the base compound used has a general formula of M(OR 6 )4, where M is Si, Al, Ti, In, Sn or Zr; and R 6 is a hydrogen, a substituted or unsubstituted alkyl group or a derivative thereof.
  • the base compound is tetraethyl orthosilicate (Si(OCH2CH3)4).
  • the water-based coating composition may include bonding agent to aid bonding of the coating to the desired surface.
  • the bonding compound used has a general formula of M(0R 7 ) R R 9 Z , where M is Si, Al, In, Sn or Ti; R 7 is a hydrogen, a substituted or unsubstituted alkyl group or derivatives thereof; R 8 is a hydrogen, a substituted or unsubstituted alkyl group or derivatives thereof; R 9 is a substituted or unsubstituted epoxy or glycidoxy group; and x and z are each independent integers from 1 to 3, y is an integer from 0 to 2, and the sum of x, y and z is 4.
  • the bonding agent is 3- glycidoxypropyltrimethoxysilane (Si(OCH3)3glycidoxy).
  • the water-based coating composition may include a plasticizer to increase or maintain elasticity of the coating to be formed.
  • the plasticizer used in the water-based coating composition has the general formula of M(OR 10 )4-I 1 where M is Si, Al, In, Sn or Ti; R 10 is a hydrogen, a substituted or unsubstituted alkyl group or derivatives thereof; and R 11 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group or a derivative thereof; and x is 1, 2 or 3.
  • the plasticizer is trimethoxypropylsilane (Si(OCH3)3CH 2 CH 2 CH3).
  • the water-based coating composition can include a chelating agent to enhance homogeneity of the organic/inorganic compounds or portions of compounds in the solution.
  • the chelating agent is an alkoxysilane, metal oxide precursor, or both having the general formula of M(0R 12 ) ⁇ R 13 ?
  • R 14 z where M is Si, Al, In, Sn or Ti;
  • R 12 includes a hydrogen, a substituted or unsubstituted alkyl group, or derivatives thereof;
  • R 13 includes a hydrogen, a substituted or unsubstituted alkyl group, or derivatives thereof;
  • R 14 includes a substituted or unsubstituted alky or alkenyl group having from 3 to 20 carbon atoms or a substituted or unsubstituted amine (including primary, secondary and tertiary) or thiol; and
  • x and z are each independently an integer from 1 to 3
  • y is an integer from 0 to 2
  • the sum of x, y, and z is 4.
  • the concentration of the base compounds, bonding agents, plasticizers, chelating agents, and/or other functional additives in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%,
  • the percentage can be calculated by weight or volume of the total composition.
  • concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
  • the waterborne virucidal/bactericidal coating composition can be prepared by: (a) obtaining at least one active compound, at least one graft polymer backbone agent, and at least one solvent, and optionally one or more base compound(s), bonding agent(s), plasticizer(s), and/or chelating agent(s); (b) adding the above mentioned ingredients to the solvent(s) to form a solution/mixture; and (c) optionally mixing the solution/mixture with water under acidic conditions (e.g., pH of 6 or less, or pH ⁇ 5) to form a homogeneous sol-gel solution.
  • acidic conditions e.g., pH of 6 or less, or pH ⁇ 5
  • the solution can be stirred at a temperature from 50 to 100 °C for between 10 seconds (fast- reactions) to 10 days (slower reactions).
  • the quaternary ammonium compound(s) or derivative(s) of such are either chemically reacted to the hydrophobic chemical agent(s) to form covalent bonds or physically entrapped/encapsulated with the materials used for the coating.
  • the waterborne virucidal/bactericidal coating composition can be prepared by emulsifying and/or homogenizing an aqueous colloidal suspension of active compound(s), graft polymer backbone agent(s), emulsifying agent(s), and optional hydrophobic agent(s), co-solvent(s), bonding agent(s), plasticizer agent(s), and/or chelating agents using either ultrasonication techniques, or preferably, using a high-pressure homogenizer or high-shear emulsifier (e.g., SIL VERSON® L5M-A).
  • SIL VERSON® L5M-A high-pressure homogenizer or high-shear emulsifier
  • the waterborne virucidal/bactericidal coating compositions can be made by a step 10 of mixing at least one cosolvent and at least one graft polymer backbone agent to form a first mixture; a step 14 of adding at least one active compound and at least one emulsifying agent to the first mixture to form a second mixture; a step 18 of adding water to the second mixture to form a third mixture comprising a colloidal suspension; and a step 22 of emulsifying the third mixture.
  • Some methods may also comprise a step 26 of adding to the second mixture a base compound, a bonding agent, a hydrophobing agent, a plasticizer, and/or a chelating agent.
  • Precursor A of typically less than 1 liter may be bath sonicated at 35 kHz in a sealed borosilicate glass, stainless steel, or hard plastic vessel for 1-2 hours at 38 °C to yield a stable mini-emulsion with sub-500-nm colloids.
  • a larger volumes of Precursor A may be homogenized in a high-shear batch emulsifier using a compatible high-shear perforated square -/circular-hole stator with a workhead of appropriate dimensions operating at between 5000 - 10,000 RPM and at temperature between 25- 90 °C for 1-5 hours in a cylindrical reaction vessel to yield a stable micro-emulsion with colloids with a mean diameter of ⁇ 2000 nm.
  • Precursor A may be homogenized/emulsified to yield a stable mini-/nano-emulsion using a suitable high-pressure homogenizer operating at pressures values between 50-200 MPa and at a temperature between 25- 90 °C. It should be noted that each particular high-shear mixing/emulsification system will accordingly require different emulsification parameters to achieve the same desired degree and dispersity of emulsification.
  • Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
  • a method of coating a substrate in need of a coating can include (a) obtaining a substrate (e.g., fabrics; porous substrates and tarps, textiles, fiber materials used for manufacturing air filters, masonry materials, or aquatic structures); and (b) applying the waterbased coating composition(s) discussed above or herein to the substrate, wherein the water-based coating composition imparts virucidal/bactericidal/biocidal and water repellent properties to the substrate.
  • Virucidal/bactericidal properties can be imparted to the outside surfaces of the substrate, impregnated in the substrate, or chemically incorporated into the substrate.
  • the water-based coating composition can be deposited on the surface of substrates by spraying, misting, doctor-blading, padding, foaming, flooding, dipping, rolling, or inkjet printing.
  • the water-based coating composition is applied by (a) contacting the substrate with a solution comprising the water-based coating composition to coat the substrate; and (b) subjecting the coated material to conditions sufficient to remove the solvents and dry the material, where at least a portion of the water-based coating composition penetrates the surface of the substrate.
  • FIG. 2 shown are some steps of the present methods of preparing the substrates coated with the waterborne virucidal/bactericidal coating compositions.
  • the waterborne virucidal/bactericidal coated-substrates can be made by a step 30 of coating a substrate with the waterborne virucidal/bactericidal coating compositions; and a step 34 of treating the coated substrate to remove the water and co-solvents and to cure the coated substrate.
  • the conditions of step 14 can include a temperature of 25 to 200 °C and/or can be sufficient to crosslink the sol-gel.
  • the waterborne virucidal/bactericidal coating composition formed on the substrate does not change the feel and texture of the substrate before coating.
  • certain cellulose semi-permeable membranes which are used in kidney dialysis, can also be potentially coated with the breathable, waterborne, virucidal/bactericidal coating compositions discussed herein that can act as a filtration device that immobilizes infectious virions/microbes.
  • the coated membrane acts in the dialysis system as a mechanism to both destroy the virus but also remove infectious virions/bacteria from the blood stream.
  • a method of inhibiting leaching of active compound(s) e.g., quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such
  • active compound(s) e.g., quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such
  • the method can include applying the waterbased coating composition described throughout the specification and drying the coated substrate.
  • the water-based coating composition inhibits leaching of active compound(s) from the substrate by forming covalent bonds between the hydrophobic chemical agent(s) and the active compound(s) of the water-based coating composition and/or physically entrapping/encapsulating the active compound(s) within the water-based coating composition.
  • the water-based coating composition described throughout the specification inhibits the leaching of active compound(s) at the efficiency of more than 95%.
  • a method of forming a coating on a substrate comprises the steps of:
  • the water-based coating composition forms an interpenetration polymer network that inhibits leaching of an active compound from the substrate by forming covalent bonds between the hydrophobic chemical agent(s) and the active compound(s) of the water-based coating composition or physically entrapping/encapsulating the active compound(s) within the waterbased coating composition, and the cured coating is flexible.
  • the method of any embodiments discussed above may further include at least one active compound that comprises a quaternary ammonium compound or derivative of such capable of destroying infectious agents/contagions, such as enveloped viruses like SARS-CoV (the virus that causes COVID- 19) and Influenza A viruses; and/or capable of destroying bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica and Pseudomonas aeruginosa.
  • infectious agents/contagions such as enveloped viruses like SARS-CoV (the virus that causes COVID- 19) and Influenza A viruses
  • enveloped viruses like SARS-CoV (the virus that causes COVID- 19) and Influenza A viruses
  • capable of destroying bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Entero
  • the quaternary ammonium compound or derivative of such of any embodiment discussed above comprises of an active cationic species with a general formula of:
  • Q is either a nitrogen or phosphorous atom and R is an aryl or alkyl group.
  • the quaternary ammonium compound of any embodiment discussed above comprises a silyl ether, alkoxysilyl, hydroxysilyl, and silyl halide quaternary ammonium/phosphonium silanes with the generalized nonlimiting formula: where Q is either a nitrogen atom or phosphorous atom, R 1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group; R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted
  • the quaternary ammonium compound of any embodiment discussed above comprises silyl ether, trialkoxysilyl, trihydroxysilyl quaternary ammonium/phosphonium compounds with a general nonlimiting formula of: where Q is either a nitrogen atom or phosphorous atom, R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl
  • the method of any embodiments discussed above may further include at least one active compound that comprises a tertiary sulfonium compound or derivative of such capable of destroying infectious agents/contagions, such as enveloped viruses like SARS- CoV (the virus that causes COVID-19) and Influenza A viruses; and/or capable of destroying bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica and Pseudomonas aeruginosa.
  • the tertiary sulfonium compound(s) or derivative(s) of such of any embodiment discussed above includes a positively charged polyatomic ion with the structure
  • R is an aryl, alkyl, phenyl, benzyl, allyl, alkenyl, or alkynyl group
  • R 1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group
  • R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted ally
  • silyl ether, trialkoxysilyl, and trihydroxysilyl tertiary sulfonium compounds of any embodiment discussed above can have a general formula of: where R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R 2 , R 3 , R 4 , and R 5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivative
  • the method of any embodiments discussed above may further include at least one active compound that comprises a polymer or derivative of such capable of destroying infectious agents/contagions, such as enveloped viruses like SARS-CoV (the virus that causes COVID-19) and Influenza A viruses; and/or capable of destroying bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica and Pseudomonas aeruginosa.
  • infectious agents/contagions such as enveloped viruses like SARS-CoV (the virus that causes COVID-19) and Influenza A viruses
  • enveloped viruses like SARS-CoV (the virus that causes COVID-19) and Influenza A viruses
  • the polymer or derivative of such of any embodiment discussed above comprises polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly ethylacry lie acid (PEAA), polypropylacrylic acid (PPAA), polyvinylbenzoic acid (PVBA), or a copolymer of any combinations of the above monomers (acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid and vinylbenzoic acid), said polymers having an average molecular weight from 25,000 to 1,000,000 Da.
  • the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents.
  • the polymers may exist in full or partially anionic forms with alkali metal counter ions (preferably sodium or potassium).
  • the method of any embodiments discussed above may further include a graft polymer backbone agent comprising an alkoxyalkylsilane wherein the alkoxyalkylsilane has a general formula of: [CH 3 (CH 2 )a]bSiR 7 c[alkoxy]d where [alkoxy] comprises methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or a combination thereof; R7 comprises a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, or derivatives thereof, and a is an integer from 0 to 20, b is the integer 1, 2, or 3, c is the integer 0, 1, 2, or 3, and d is the integer 1, 2, or 3, provided that the sum of b. c and d equals 4.
  • the graft polymer backbone agent of any embodiment discussed above comprises at least one functional silicone/siloxane in oligomer/co-oligomer form, polymer/co-polymer form, or a combination thereof having a nonlimiting generalized formula of: with an average molecular weight between 100 to 100,000 Da and an average viscosity between 10 to 20,000 mPa- s, where R a , R b , R c , R d , R e , R f , R g , and R h are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alken
  • X and X’ are an alkoxy group, hydroxyl group, halogen, hydrogen, vinyl group, mercapto/thiol group, amine group, epoxide group, unsubstituted/substituted alkene group, unsubstituted/substituted alkyne group, unsubstituted/substituted allyl group, unsubstituted/substituted alkynyl group, unsubstituted/substituted alkenyl group, an unsubstituted/substituted alkyl group, or a combination thereof, where X and X’ may be the same or dissimilar, z and j are integer values between 1-200,000, where z and j may or may not be equal to one another.
  • the graft polymer backbone agent of any embodiment discussed above may include one or more substituted/unsubstituted alkyl-functional silyl ether, halogensilane, or silylhydride of the generalized structure: where R a , R b , R c , and R d are each independent hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, an alkoxy group, a hydroxyl group, a hydrogen atom, or a halogen, where R a , R b , and R c may be the same or dissimilar so long as there exists at least one
  • the method of any embodiments discussed above may further include a solvent used to disperse all the components to form a homogeneous solution/emulsion.
  • the solvent may include methanol, ethanol, phenoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol acetone, acetonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, di(propylene glycol)methyl ether, 4- chlorobenzotrifluoride, odorless mineral spirits/petroleum distillates, or a mixture/combination thereof.
  • the waterborne virucidal/bactericidal coating composition can be prepared by (a) obtaining at least one active compound, at least one graft polymer backbone agent, and at least one solvent, and optionally, one or more base compound, bonding agent, plasticizer and/or chelating agent; (b) adding the above mentioned ingredients to the solvent(s) to form a solution/mixture; and (c) optionally mixing the solution/mixture with water under acidic conditions (e.g., pH of 6 or less, or pH ⁇ 5) to form a homogeneous sol-gel solution.
  • the solution can be stirred at a temperature from 50 to 100 °C for between 10 seconds (fast-reactions) to 10 days (slower reactions).
  • the quaternary ammonium compound(s) or derivative(s) of such are either chemically reacted to the hydrophobic chemical agent(s) to form covalent bonds or physically entrapped/encapsulated with the materials used for the coating.
  • the waterborne virucidal/bactericidal coating composition can be prepared by emulsifying and/or homogenizing an aqueous colloidal suspension of active compound(s), graft polymer backbone agent(s), emulsifying agent(s), and optional hydrophobic agent(s), co-solvent(s), bonding agent(s), plasticizer agent(s), and/or chelating agents using either ultrasonication techniques, or preferably, using a high-pressure homogenizer or high-shear emulsifier.
  • a high-shear batch mixer may be used to mechanically emulsify/homogenize the aqueous colloidal suspension of active compound(s), graft polymer backbone agent(s), emulsifying agent(s), and optional hydrophobing agent(s), co-solvent(s), bonding agent(s), plasticizer agent(s), and/or chelating agents by shearing at operating frequencies between 5,000-10,000 RPM and at temperature between 25-90 °C for between 1-5 hours, until the desired mean colloid diameter and dispersity is achieved.
  • Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
  • a method of inhibiting leaching of active compound(s) from a substrate is disclosed.
  • the method can include applying the waterbased coating composition described throughout the specification and drying the coated substrate.
  • the water-based coating composition inhibits leaching of active compound(s) from the substrate by forming covalent bonds between the hydrophobic chemical agent(s) and the active compound(s) of the water-based coating composition and/or physically entrapping/encapsulating the active compound(s) within the water-based coating composition.
  • the water-based coating composition described throughout the specification inhibits the leaching of active compound(s) at the efficiency of more than 95%.
  • the method of any embodiments discussed above includes substrates that are functionalizing porous plastics, tarpaulin, synthetic/organic fibers such as those used in manufacturing fabric, linens, garments, and mask, fiber materials used for manufacturing air filters (for heating, ventilation, air conditioning, filters for buildings, cars, boats, planes, filtration in dialysis and other biological instruments).
  • substrates may also include masonry, concrete, stone, brick, stucco, grout, wood-based products, fences, decks, furniture and porous ornaments or other porous structures.
  • the waterborne virucidal/bactericidal coating composition formed on the substrate does not change the feel and texture of the substrate before coating.
  • AATCC Test Method 193-2012 (Aqueous Liquid Repellency (ALR): Water/Alcohol Solution Resistance Test).
  • ARR Aqueous Liquid Repellency
  • the test is conducted by placing a minimum of three 0.050 mL drops of solution, beginning with the lowest numbered test solution, and spaced ⁇ 4.0 cm apart from one another with the applicator tip held at a height of ⁇ 0.60 cm above the surface of a flat test specimen.
  • the test solution In order to receive a passing grade, the test solution must remain on the surface of the test specimen for 10 ⁇ 2.0 seconds without darkening, wetting, or wicking into the fibers of the test specimen.
  • the aqueous liquid repellency grade of the test specimen is the highest numbered test solution that receives a passing grade.
  • ASTM E 2149-13a Standard Test Method for Determining the Antimicrobial Activity of Antimicrobial Agents Under Dynamic Contact Conditions. The purpose of this test method is to perform the leaching procedure on fabrics treated with the water-based virucidal/bactericidal coating and obtain leachates that are further analyzed by ASTM D5806-95 (2017).
  • the leaching apparatus is a loose tea-leaf steeper atop a beaker containing deionized water.
  • the cured fabric sample treated with the water-based virucidal/bactericidal coating is neatly folded and placed at the bottom of the apparatus.
  • the cap of the leaching apparatus contains a depressor to ensure the sample remains submerged throughout the leaching process.
  • the steps of the leaching procedure are as follows: 1) Carefully place the leaching apparatus on a beaker containing 275 mL deionized water. 2) Set the stirrer/hotplate to 1100 rpm and 35 °C and start the timer for 1 hour. 3) After 1 hour, carefully remove the apparatus and collect the leachate for the leaching experiment. A more aggressive leaching process is also carried out by using 275 mL non-ionic sulfactant MAKON® DA-4 (0.02 v/v %) in deionized water instead.
  • the purpose of this test method is to determine the concentration of the active quaternary ammonium compound in the leachate by titration with sodium lauryl sulfate. All reagents were prepared as prescribed in ASTM D5806-95 (2017).
  • 100 mL analyte leachate from leaching experiment per ASTM E2149
  • the final solution is potentiometrically titrated with 8.39 x 10’ 3 N sodium lauryl sulfate and the volume of titrant (SLS) used to completely titrate the nitrate ions
  • the detection limit in the current experimental setup using a HANNATM HI931 Automatic Potentiometric Titrator equipped with HI4113 Nitrate Combination electrode is about 10 ppm for all three quaternary ammonium compounds: BENZETHONIUM CHLORIDE (used as the titration standard) (CAS#: 121-54-0), DIMETHYLOCTADECYL[(3- TRIHYDROXYS IL YL) PROPYL] AMMONIUM CHLORIDE (CAS#: 199111-50-7) and DIMETHYLOCTADECYL[(3-TRIMETHOXYSILYL)PROPYL] AMMONIUM CHLORIDE (CAS#: 27668-52-6).
  • a precursor solution of methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane (CAS: 102782-92-3/75718-16-0) (i.e., poly(3-((2- aminoethyl)amino)propyl)methyl(dimethyl)siloxane) in a co-solvent blend of methyl acetate, 4- chlorobenzotrifluoride, and dimethyl carbonate was prepared under stirring (Precursor A).
  • a designated amount of Precursor A was heated to a temperature of 40 °C under stirring.
  • bonding agent (3-glycidoxypropyl)trimethoxysilane was added to initiate nucleophilic addition with primary amine groups of the graft polymer backbone agent via an SN2-type epoxide ring-opening mechanism.
  • hydrophobing and plasticizer agent n-propyltrimethoxysilane was added followed by designated amounts of nonionic emulsifying agent di(propylene glycol)monomethyl ether.
  • the resulting colloidal suspension (Precursor C) was mechanically emulsified using either ultrasonication techniques, or preferably, using a high-pressure homogenizer or high-shear emulsifier (e.g., Silverson L5M-A).
  • a larger volume of Precursor C was homogenized in a high-shear batch emulsifier using a high- shear perforated square-hole stator with a 2.5-inch diameter workhead operating at between 5,000 - 10,000 RPM and at temperature between 25 - 60 °C for 90 minutes in a cylindrical HDPE vessel to yield a stable micro-emulsion with colloids of a mean diameter of 2000 nm.
  • Mini- emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
  • the aforementioned final water-based solution was then used to treat two separate fibrous materials; namely, 100% cotton fabric and a cotton/polyester blend fabric.
  • the fibrous substrate materials were treated with the solution by immersing the samples in a solution bath. After fully wetting the samples, excess solution was removed by suspending the saturated sample in the air until enough solution was drained from the sample to attain a target %-weight pick-up ranging between 125 - 150 % (wt./wt.).
  • the samples were then allowed to air dry/cure for 30 minutes under a hot-air blower at 40 °C, cured in a forced-draft oven at 80 °C for 30 min, then acclimated to room conditions for 30 minutes prior to efficacy evaluation.
  • AATCC Test Method 193-2012 The following test methods were conducted to evaluate the surface energy of the treated samples at the air-fiber materials interface: AATCC Test Method 193-2012. Correspondingly, treated samples received a mean ALR grade of 4 on 100% cotton fabric and a mean ALR grade of 4 on a cotton/polyester blend fabric. All treated fabric samples remained soft to the touch with excellent post-treatment hand of fabric.
  • a precursor solution of methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane (CAS: 102782-92-3/75718-16-0) (i.e., poly(3-((2- aminoethyl)amino)propyl)methyl(dimethyl)siloxane) in a co-solvent blend of methyl acetate, 4- chlorobenzotrifluoride, and dimethyl carbonate was prepared under stirring (Precursor A).
  • a designated amount of Precursor A was heated to a temperature of 40 °C under stirring.
  • bonding agent (3-glycidoxypropyl)trimethoxysilane was added to initiate nucleophilic addition with primary amine groups of the graft polymer backbone agent via an SN2-type epoxide ring-opening mechanism.
  • hydrophobing and plasticizer agent n-propyltrimethoxysilane was added followed by designated amounts of nonionic emulsifying agent di(propylene glycol)monomethyl ether.
  • the resulting colloidal suspension (Precursor C2) was mechanically emulsified using ultrasonication techniques.
  • Precursor C2 was bath sonicated at 35 kHz in a sealed borosilicate glass vessel for 1 hour at 38 °C to yield a stable mini-emulsion with sub- 500-nm colloids.
  • Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
  • the aforementioned final water-based solution was then used to treat two separate fibrous materials; namely, 100% cotton fabric and a cotton/polyester blend fabric.
  • the fibrous substrate materials were treated with the solution by immersing the samples in a solution bath. After fully wetting the samples, excess solution was removed by suspending the saturated sample in the air until enough solution was drained from the sample to attain a target %-weight pick-up ranging between 125 - 150 % (wt./wt.).
  • the samples were then allowed to air dry/cure for 30 minutes under a hot-air blower at 40 °C, cured in a forced-draft oven at 80 °C for 30 min, then acclimated to room conditions for 30 minutes prior to efficacy evaluation.
  • a precursor solution of methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane copolymer (CAS: 102782-92-3/75718-16-0) (i.e., poly(3- ((2-aminoethyl)amino)propyl)methyl(dimethyl)siloxane) in a co-solvent blend of methyl acetate, 4-chlorobenzotrifluoride, and dimethyl carbonate was prepared under stirring (Precursor A). A designated amount of Precursor A was heated to a temperature of 40 °C under stirring.
  • bonding agent (3-glycidoxypropyl)trimethoxysilane was added to initiate nucleophilic addition with primary amine groups of the graft polymer backbone agent via an SN2-type epoxide ring-opening mechanism.
  • hydrophobing and plasticizer agent n-propyltrimethoxysilane was added followed by designated amounts of nonionic emulsifying agent di(propylene glycol)monomethyl ether.
  • nonionic emulsifying agent isodecyl alcohol ethoxylate (CAS: 78330-20-8) was added followed by specific amounts of active compound octadecyldimethyl(3-trihydroxysilylpropyl)ammonium chloride (CAS: 199111-50-7) (i.e., polysilsesquioxane steardimonium chloride) in oligomeric/polymeric powdered form, where bath ultrasonication at 35kHz for 2 minutes was used to wet and disperse the polysilsesquioxane steardimonium chloride powder. A single-phase, homogeneous, translucent solution was obtained (Precursor B3).
  • Precursor B3 After 2 minutes, all added deionized water was slowly added to Precursor B3 at a rate of ⁇ 20 mL/s under vigorous stirring. A white, turbid, macroscale, homogeneous colloidal suspension was immediately obtained with a pH between 5.5 and 7 - no indication of flocculation or aggregation was observed.
  • the resulting colloidal suspension (Precursor C3) was mechanically emulsified using ultrasonication techniques.
  • Precursor C3 was bath sonicated at 35 kHz in a sealed borosilicate glass vessel for 1 hour at 38 °C to yield a stable mini-emulsion with sub- 500-nm colloids.
  • Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
  • the aforementioned final water-based solution was then used to treat two separate fibrous materials; namely, 100% cotton fabric and a cotton/polyester blend fabric.
  • the fibrous substrate materials were treated with the solution by immersing the samples in a solution bath. After fully wetting the samples, excess solution was removed by suspending the saturated sample in the air until enough solution was drained from the sample to attain a target %-weight pick-up ranging between 125 - 150 % (wt./wt.).
  • the samples were then allowed to air dry/cure for 30 minutes under a hot-air blower at 40 °C, cured in a forced-draft oven at 80 °C for 30 min, then acclimated to room conditions for 30 minutes prior to efficacy evaluation.
  • AATCC Test Method 193-2012 The following test methods were conducted to evaluate the surface energy of the treated samples at the air-fiber materials interface: AATCC Test Method 193-2012. Correspondingly, treated samples received a mean ALR grade of 4 on 100% cotton fabric and a mean ALR grade of 4 on a cotton/polyester blend fabric. All treated fabric samples remained soft to the touch with excellent post-treatment hand of fabric.
  • Filtering SARS-CoV-2 Initial investigation of viral transmission was done on a MVTR-A1 -treated tri-pleat air filter having a Minimum Efficiency Reporting Value (MERV) of 8 (“treated MERV 8”), an untreated tri-pleat air filter having a MERV of 8 (“untreated MERV 8”), and an untreated tri-pleat air filter having a MERV of 13 (“untreated MERV 13”).
  • MERVs report a filter’s ability to capture larger particles between 0.3 and 10 microns (pm). This value is helpful in comparing the performance of different filters.
  • the rating is derived from a test method developed by the American Society of Heating, Refrigerating, and Air Conditioning Engineers (ASHRAE). The higher the MERV rating the better the filter is at trapping specific types of particles.
  • ASHRAE American Society of Heating, Refrigerating, and Air Conditioning Engineers
  • Embodiments of the disclosure having a coated substrate may refer to a filter for HVAC applications with an applied coating according to one or more embodiments of this disclosure similar to the experimental filter configuration of FIG. 3.
  • Collection and retention filter swatches (FPR-10) were eluted in 100 mL of 1% beef extract/0.05M glycine (pH 9) for 20 min. The eluent was concentrated to a final volume of 1.6 mL using a combination of tangential flow filtration and centrifugal ultrafiltration. Subsequently, 50 pL of each sample was treated with 6.5 pL of
  • RT-qPCR was conducted using 7 pL samples in triplicate using a Chai Open qPCR instrument (Chai, Inc.). Gloves were changed between samples to minimize cross-contamination.
  • a larger cycle quantification value (C q ) indicates a smaller initial concentration of captured thermally-inactivated SARS-CoV-2 virions extracted from the collection filter, which corresponds to an increase in virion-filtration performance.
  • the data demonstrate that as the MERV rating increases, the cycle quantification requires a larger number of amplification/denaturation cycles before onset of fluorescence, as less viral load penetrates the experimental filters. The treated filters are far more effective than even the MERV 14 and substantially reduce transmission to a negligible rate, as shown in FIG. 5.
  • Cycle quantification values were also compared to filter efficiency, as shown in FIG. 6.
  • the x-axis represents MERV ratings for different filters
  • the left y-axis is the cycle quantification value
  • the right y-axis represents the theoretical efficiency of the filters when dealing with virions smaller than 0.3 pm.
  • Two lines are shown, with the first line (•) depicting the actual cycle quantification values determined and the second line ( — ) representing a theoretical estimation of the cycle quantification values that the filters should yield depending on the efficiency of the filter.
  • This data shows that the performance of MVTR-A1 -treated MERV 8 filter performs equivalent to or better than what would be expected for a MERV 14 or 16 filter.
  • the flow rate is determined by diameter of the particle size, viscosity of the fluid, and speed of the fluid through the air.
  • the particles traveling in an aqueous medium through the air drift through the filters, they are governed by factors including drag force, comprising fluid or friction resistance, and are thus impacted by the in-path filter.
  • drag force comprising fluid or friction resistance
  • the pressure drops along the contact length between the fiber boundaries and flow of the fluid and particle (also known as the Bejan number), as does the momentum and mass diffusivity (also known as the Schmidt number). If the particles or the droplets are larger than 10 pm, they will most likely impact on the surface of the filter fibers.
  • the filter efficiency continues to decrease, as shown in FIG. 8, until particle size decreases below the penetrating particle size for most filter systems — less than 120 nm.
  • the graph of FIG. 8 shows several lines corresponding to filter efficiency. The bottom line corresponds to MERV 6, which each higher line sequencing through MERV 8, 11, 12, 13, 14, 15, and 16 for the top-most line.
  • the challenge is that the virus is too large for the Peclet number to affect its passage and, in some embodiments, the virus may be filtered like solid state particles normally handled by MERV 13-16 filters.
  • K n » particles follow along the slip regime, while for K n « 1, particles follow along molecular free flow.
  • the K n value is ⁇ 1.1, which results in particles that are much more likely to follow molecular free flow of air, implying closeness to diffusion transitions instead of particles affected by interception filtration.
  • Table 1 uses data from the FIG. 9 to determine where the filter efficiency overlaps with the particle size of SARS-CoV-2. Even with the highest-rated filter, there is still a risk the virus will pass through — it would take 3 or 4 passes of the same air through the same filters to clean the air almost completely and remove the risk of passing on the virus.
  • the O-PTIR+R technique was non-contact and utilized tunable pulsed mid-IR laser light (5.5 - 12 pm) from a QCL to excite a selected spot on a sample under ambient conditions, producing transmission-mode FTIR-quality spectra at submicron spatial resolution.
  • IR absorbance is measured through energy and position changes in scattered 532-nm laser light due to localized shifts in refractive index from the sample at laser foci.
  • O-PTIR+R bypasses the wavelength-dependent diffraction limit of IR light (5 - 12 pm) and resolves interfacial regions with submicron resolution and remarkable chemical specificity.
  • Averaged O-PTIR spectra of pristine/untreated and treated cotton are provided in FIG. 9A.
  • Averaged Raman spectra of pristine/untreated and treated cotton are provided in FIG. 9B.

Abstract

A non-leaching, biocompatible, non-cytotoxic, breathable, water-based virucidal/bactericidal coating/carrier composition can be used to treat porous or nonporous substrates to provide protection against infectious agent(s)/contagion(s)/pathogen(s) that cause infectious diseases, such as COVID-19, via mechanisms-of-action that include but are not limited to deactivation, inhibition, termination, and/or lysis of the infectious agent(s)/contagion(s)/pathogen(s). The coating composition includes one or more active compounds, graft polymer backbone agents, and emulsifying agents. The active compound(s) in the coating compositions may potentially include derivatives of quaternary ammonium/phosphonium compounds, tertiary sulfonium compounds, polyionic compounds, metal salts, metal nanoparticles, metal-oxide nanoparticles, reactive oxygen-generating species, N-halamines, and/or biomacromolecules acting as immobilized virucidal/bactericidal agents.

Description

NON-LEACHING WATERBORNE VIRUCIDAL/BACTERICIDAL COATING
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 63/073,615 to Curran et al., filed on September 2, 2020, and entitled “Non-Leaching Waterborne Virucidal/Bactericidal Coating Compositions and Uses Thereof,” which is incorporated by reference herein.
FIELD OF THE DISCLOSURE
[0002] This disclosure relates to water-based virucidal/bactericidal coating compositions. More specifically, portions of this disclosure relate to non-leaching, biocompatible, non-cytotoxic, breathable, water-based virucidal/bactericidal coating compositions that also renders the coated surface permanently hydrophobic, and uses thereof, including but not limited to air-filtration media.
BACKGROUND
[0003] Over the years, much effort has been directed to solving the problem of imparting resistance/inhibition against infectious/viral diseases like COVID- 19, MERS, or SARS to fabrics, textiles, fibers, garments, filters, plastics, porous substrates, and tarpaulin-type materials. Other substrates may also include masonry, concrete, stone, brick, stucco, grout, wood-based products, fences, decks, furniture and porous ornaments. While the use of melt blown fabrics is somewhat effective in preventing the transmission of infectious microbes or viruses, after use they must be disposed of carefully - as quite often the infectious agent is still infectious, transmissible, and capable of cross -contamination. These materials do not deactivate/kill viruses/bacteria, but instead act merely as a physical barrier. The infectious nature of viruses/bacteria means any surface contaminated by them potentially becomes an active incubation site.
[0004] Current treatments to mitigate the transmission of infectious agents/diseases in hospitals, homes, schools, apartments, offices, and public spaces, including all germane surfaces in such shared/non-exclusive areas, require vigorous daily treatments with antiviral/anti-infectious agents such as surface cleaners, using some form of detergent, an alcohol solution with at least 70% ethyl alcohol and most commonly registered household disinfectants (e.g., benzalkonium chlorides or alkyl ammonium chlorides), including peroxides, sodium hypochlorite, and chlorine dioxide.
[0005] When dealing with fabrics after their exposure to infectious agents like SARS-CoV-2, it is common practice to wash the fabric(s) in near boiling/boiling hot water; when possible, it is an additional precaution to use antiviral soaps and detergents with the fabrics. If the fabrics cannot be washed immediately, then they should be disposed of immediately, and in fact this is quite often the case for most, if not all, Personal Protective Equipment (PPE). All too often, crosscontamination between fabrics, material surfaces, and even health care personnel may occur because the infectious agent/pathogen remains transmittable. Further, once washed, the fabrics still must be thoroughly dried.
[0006] When around others or in regions where the infectious agent(s)/contagion(s) may have traveled to, it is always best to wear PPE to mitigate transmission/cross contamination of such infection agent(s)/contagion(s). Standard practices regarding PPE in healthcare environments entails the use of disposable gloves and gowns that have to be taken off immediately after use for disposal. While there are multiple reasons for this, the principle influencing factor is the risk of contaminated PPE containing infectious agent(s)/contagion(s) cross contaminating other surfaces and facilitating transmission. In addition, if there are any breaches in the PPE (holes, tears, exposure through poor fitting or failure of the protective membranes), that can also lead to dire circumstances which can lead to cross contamination of infectious agent(s)/contagion(s). These breaches have to be reported, and the person who has been exposed must then be examined carefully for potential transition from the caregiver to another patient or the like. For crosscontamination or accelerated transmission to occur the infectious agent(s)/contagion(s) need to breach the protective measure in place. To prevent that from happening, individuals face the difficult task of protecting all surfaces at all times and carefully managing interactions.
[0007] Even when surfaces are treated with some form of antimicrobial or disinfectant to prevent the transmission or cross-contamination of infectious agents or viruses, such as SARS- CoV-2, these treatments usually involve short-term solutions, such as immediate disinfection with irradiation, as opposed to something that is far more long-term or permanent. Unless the treatment is permanently locked in place or immobilized, due to the nature of certain infectious agents/contagions being non-water soluble and resistant to chemical cleaners, such infectious agent(s)/contagion(s) may remain active and potentially cross -contaminate other surfaces or transmit to a host at some stage.
[0008] Substrates including fabrics and filters therefore not only require a liquid repellent, as the medium by which many infectious agent(s)/viruses travel is largely aqueous, but also an active compound(s) to deactivate/lyse any infectious agent that comes into contact with the substrate surface before it becomes a transmissible contagion. While such protective measures are critical for decreasing transmission of infectious agents/contagions, current chemical treatments do not provide such a solution.
SUMMARY
[0009] Surfaces treated to prevent liquid from “wetting” the substrate (thus “waterproofing” the substrate) and protect the substrate from the consequences caused by the wetting (e.g., stain from dyes/pigments or water damage) has some benefits. However, the solutions to treat materials can be further improved to include one or more functional additives that can add further benefits to the resulting hydrophobic coating, such as other functional additives to alleviate damage from weathering (caused by, e.g., both natural-/artificial-radiation, antifungals, antibacterials). The coating can either penetrate porous substrates, be layered on tarpaulin-type materials, and/or be bonded to fibers such as those used in fabrics/textiles and imparts surface(s) of the coated substrate with active compound(s) that cause damage to the capsid/outer envelope protein layer, spike protein, or a process that could eventually lead to forms of viral/bacterial de-activation or lysis. In particular, hydrophobic water-based coating composition(s) can be used to treat substrates to inhibit viral/bacterial contamination, such as transmittal from human to human, animal to human (e.g., zoonotic diseases/zoonosis), human to animal, and/or via surface contact and/or deposition onto surfaces, fabrics, and other porous substrates that are shared to any extent (e.g., various substrates that may come into contact with more than one human/animal).
[0010] In some instances it may be preferable to have a surface that is hydrophilic in nature, in particular when it comes to coating face masks or filters used in, for example, medical treatments and HVAC systems. Outside of the host, human infectious agent(s)/contagion(s) typically transmit and propagate either directly via contact with static/airbome infectious respiratory droplets, bodily fluids, or excrement, as well as indirectly via contact with fomites, vectors, or contaminated commonly touched objects/surfaces in the environment. When looking at respiratory aerosols, which travel through the air, transmission of infectious agent(s)/contagion(s) can depend on droplet size transmitted through regular respiration, coughing, or sneezing. During the mechanism of coughing and sneezing, droplet formation can occur in a number of ways, including shear stress and dynamic compression along the mucus-air interface, which dislodges mucus and results in the formation of small droplets. Respiratory droplet formation characteristics are dependent mainly on place of origin. Large droplet formation is typically a consequence of oral cavity expulsion (-50- 100 pm) whereas smaller droplets are formed when they originate from the bronchioles (~0.6 - 16 pm), although the presence of viral infections can alter the droplet size.
[0011] The fundamental principle of using filters to capture respiratory droplets or particles containing infectious agent(s)/contagion(s) is based on the fiber weave of the filter and its interconnectedness and thickness, the incoming flow of air and particulates, and the aerosol properties of the droplets or particles. The pathways used by particulates inside the filter weave and through the filter fibers are based on flow properties including inertial impaction, interception, and diffusion mechanisms. Large particles ranging from 60-100 pm fall to the ground due to gravity after 2 meters, which may take only -10 seconds, although will be readily stopped at a filter if expelled towards the filters. These large droplets are carried further away when they are expelled at high velocity, such as with coughs and sneezes. They account for -35-40% of the total emission expected from a cough or sneeze. Medium-sized particulates are greater than 10 pm and impact the surface of the filter where inertial impact and adhesion forces such as electrostatic, capillary, and Van Der Waals forces cause the particles to be collected on the surface of the fibers. Smaller particulates such as those -10 pm, which remain surround by aqueous media, could stay in the air for as long as 15 minutes. These particles can be intercepted by the filter when they come within one radius of the surface of the fiber for a sufficient time to become trapped. Very small sub-5 pm diameter particles are dominated by Brownian motion and can stay airborne for many hours. These particles can be knocked off a streamline path, which would allow them to escape capture by the filter fibers.
[0012] It is the last group of aerosolized particulates that are the cause for the greatest concern when looking at transmission through face masks or rooms and buildings that are connected by HVAC systems. The water-based coating composition(s) disclosed herein may be designed to exhibit an affinity towards infectious virions with a hydrophilic surface chemistry and facilitate spreading and absorption of the infectious respiratory droplets and/or respiratory droplet nuclei in which they exist outside the host to maximize the surface area and optimize interfacial interactions between the infectious virions/microbes and active compound(s), acting both as a filter and virucide/bactericide.
[0013] When applied on membrane materials (e.g., cellulose-based virion retentive filters), the coatings described herein may likewise be used as a filtration system for the blood stream. Certain infectious virions are attracted to the oxygen in blood and as such can successfully exist even outside the human respiratory system. The treated membranes act as a mechanism to clean blood of the infectious species. Samples of these filters can then be analyzed to determine the presence of the infectious virions/microbes using optical techniques where distinctive optical fingerprinting can be carried out, thereby determining the presence and relative concentration of the infectious virions/microbes .
[0014] Embodiments of this disclosure include non-leaching, biocompatible, non-cytotoxic, breathable, water-based virucidal/bactericidal coating compositions that also render the coated surface permanently hydrophobic, and uses thereof, including but not limited to air-filtration media. Such coating compositions include one or more active compounds, graft polymer backbone agents, and emulsifying agents. The active compound(s) in the coating compositions may potentially include derivatives of quaternary ammonium/phosphonium compounds, tertiary sulfonium compounds, polyionic compounds, metal salts, metal nanoparticles, metal-oxide nanoparticles, reactive oxygen-generating species, N-halamines, and/or bio macromolecules acting as immobilized virucidal/bactericidal agents. The functionality of the active compound(s) may electively include virucidal/bactericidal properties but are not restricted exclusively to such biocidal activity. The virucidal/bactericidal coating compositions are water-borne and may include one or more solvents/co- solvents. The virucidal/bactericidal coating compositions described herein may potentially include one or more tagging agents. The tagging agent(s) may potentially include but not limited to sulphonated multi-block copolymers and silane-capped copper nanoclusters. Using tagging agents, the molecules or changes to their structures are detectible by advanced and/or combinatory spectroscopy techniques such as infrared, fluorescence tagging, and Raman spectroscopies as a diagnostic tool to detect the presence of infectious species- specific virions and/or microbes.
[0015] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only, and are not restrictive of the invention, as claimed. In this application, the use of the singular includes the plural, the word “a” or “an” means “at least one”, and the use of “or” means “and/or”, unless specifically stated otherwise. Furthermore, the use of the term “including”, as well as other forms, such as “includes” and “included”, is not limiting. The use of “/” shall be understood to be mean “and,” “or,” “and/or,” and “combinations thereof.” [0016] The terms “water-based” or “water-borne” as used herein refer to aqueous coating compositions with a water concentration greater than or equal to 25% of the net coating composition by volume.
[0017] The term “hydrophobic” refers to a property of a material where the material impedes the wetting and/or absorption of water or water-based liquids. In general, a material lacking affinity to water may be described as displaying “hydrophobicity”.
[0018] The term “hydrophilic” refers to a property of a material where the material exhibits the tendency to mix with, dissolve in, or attract the wetting and/or absorption of water or waterbased liquids. In general, a material exhibiting affinity to water may be described as displaying “hydrophilicity”.
[0019] The terms “virucidal”, “antiviral”, “viral resistant”, or “viral reduction” refer to the ability of a material to deactivate, inhibit, and/or lyse viruses; inhibit/thwart transmission of infectious agents/contagions, or minimize host-cell damage, transformation, growth, nucleation, twinning, reproduction of the infectious agent/pathogen/contagion. In some aspects, this also encompasses the ability of a material to resist the attack or layering (settling on the surface) of infectious agents/contagions like enveloped viruses, including SARS-CoV-2, Influenza A viruses, and Ebola viruses.
[0020] The terms “bactericidal”, “antibacterial”, “bacterial resistant”, or “bacterial reduction” refer to the ability of a material to destroy bacteria; resist entrance of bacteria, or suppress bacterial growth or reproduction. More specifically, it also refers to the ability of a material to resist the attack of bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica, and Pseudomonas aeruginosa. [0021] The term “antimicrobial” is a term used to describe any applicable surface or material that has been coated, sealed, or treated to impart the ability to kill microorganisms (i.e. “microbicidal”) and substantially inhibit their growth. The United States Environmental Protection Agency (EPA) states this use as to disinfect, sanitize, reduce, or mitigate growth or development of microbiological organisms. Generally, the application is to protect against bacteria and viruses. Indeed, as a more specific designation, one may also define and differentiate the microbe(s) being killed such as, for example, SARS-CoV-2, then term would be specifically antiviral. A surface or material that exhibits limited antimicrobial behavior or properties is said to be “microbial resistant”. Specifically, the material may be seen to inhibit or impede the rate at which microbes proliferate on or attach to a surface.
[0022] The terms “anti-COVID” and “COVID-resistance” are defined as a property exhibited by specifically-designed functional coatings or functionalized/chemically-modified surfaces that either inhibit or aid in the removal of a select assortment of human coronaviruses (COVIDs).
[0023] The term “C OVID -contaminated” refers to the undesired settlement, anchoring, and/or colonization of the aforementioned COVID agents on the surfaces or internal components of COVID agents adhered to fabrics used in personal protective equipment in hospitals or care facilities.
[0024] The term “breathable” as used herein refers to a material having a water vapor transmission rate of at least about 300 grams/m2/24 hours.
[0025] The coatings discussed herein can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase “consisting essentially of,” in one non-limiting aspect, a basic and novel characteristic of the coatings are their abilities to provide antibacterial, antiviral, or antimicrobial properties and water repellency for a substrate, which inhibits leaching of the active compound from the substrate.
[0026] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The following drawings illustrate by way of example and not limitation. For the sake of brevity and clarity, every feature of a given structure is not always labeled in every figure in which that structure appears. Identical reference numbers do not necessarily indicate an identical structure. Rather, the same reference number may be used to indicate a similar feature or a feature with similar functionality, as may non-identical reference numbers.
[0028] FIG. 1 illustrates a method of forming a substrate coating according to some embodiments of the disclosure.
[0029] FIG. 2 illustrates a method of treating a substrate with a coating according to some embodiments of the disclosure.
[0030] FIG. 3 is a schematic of a filter for capturing SARS-CoV-2 using a coating according to one of the embodiments of this disclosure.
[0031] FIG. 4A is a graph of relative fluorescence curves after 45 amplification/denaturation polymerase chain-reaction cycles (right) for pristine/untreated MERV 8 and MERV 13 filters against a MVTR-A1 -treated MERV 8 filter according to one of the embodiments of this disclosure. [0032] FIG. 4B is a graph of relative fluorescence values after 45 amplification/denaturation polymerase chain-reaction cycles (right) for pristine/untreated MERV 8 and MERV 13 filters against a MVTR-A1 -treated MERV 8 filter according to one of the embodiments of this disclosure. [0033] FIG. 5 provides cycle quantification values of untreated MERV 8, 11, 13, and 14 filters compared against a MVTR-A1 -treated MERV 8 filter after 45 amplification/denaturation cycles according to one of the embodiments of this disclosure.
[0034] FIG. 6 shows theoretical filter efficiency mapped against actual and equivalent cycle qualification values for a MVTR-A1 -treated MERV 8 filter and MERV 6-16 filters according to one of the embodiments of this disclosure, where experimental data corresponding to data points was obtained for untreated MERV 8-14 filters.
[0035] FIG. 7 provides cycle quantification values versus time according to one of the embodiments of this disclosure, where swabs of “captured” virus were taken of the front face of a filter.
[0036] FIG. 8 is a diagram showing fractional efficiency against particle diameter according to one of the embodiments of this disclosure.
[0037] FIG. 9A provides averaged optical-photothermal infrared (O-PTIR) spectra data for pristine/untreated cotton and MVTR-A1 -treated cotton according to one of the embodiments of this disclosure.
[0038] FIG. 9B provides averaged Raman spectra data for pristine/untreated cotton and MVTR- Al -treated cotton according to one of the embodiments of this disclosure.
DETAILED DESCRIPTION
[0039] In general, it will be understood that the illustrations are for the purpose of describing particular implementations of the disclosure and are not intended to be limiting thereto. While most of the terms used herein will be recognizable to those of ordinary skill in the art, it should be understood that when not explicitly defined, terms should be interpreted as adopting a meaning presently accepted by those of ordinary skill in the art.
[0040] Embodiments of the disclosure may be used in non-leaching, biocompatible, non- cytotoxic, breathable, water-based virucidal/bactericidal coating/carrier compositions and methods of using/applying the composition(s) to treat porous or nonporous substrates to provide protection against infectious agent(s)/contagion(s)/pathogen(s) that cause infectious diseases, such as COVID- 19, via mechanisms-of-action that include but are not limited to deactivation, inhibition, termination, and/or lysis of the infectious agent(s)/contagion(s)/pathogen(s). The coating composition includes one or more active compounds, graft polymer backbone agents, and emulsifying agents. The active compound(s) in the coating compositions may potentially include derivatives of quaternary ammonium/phosphonium compounds, tertiary sulfonium compounds, polyionic compounds, metal salts, metal nanoparticles, metal-oxide nanoparticles, reactive oxygen-generating species, N-halamines, and/or biomacromolecules acting as immobilized virucidal/bactericidal agents. The virucidal/bactericidal coating compositions are water-borne and may or may not include one or more solvents/co- solvents. The coating composition is either hydrophilic or hydrophobic and is suitable for treating/coating/functionalizing porous/nonporous substrates, including but not limited to functionalization of porous plastics, layering on tarpaulinsubstrates, and coating/functionalizing synthetic/organic fibers such as those used in manufacturing fabrics, textiles, linens, garments, personal protective equipment, masks, respirator masks, and fiber materials used for manufacturing air filters (for heating, ventilation, purification, and air conditioning as well as biological based applications in filters used in systems such as dialysis). Other substrates may also include masonry, concrete, stone, brick, stucco, grout, woodbased products, fences, decks, furniture, and porous ornaments. The changes in the fabrics or treated surfaces due to viral/bacterial presence may also be detected using spectroscopy techniques using either hand-held or bench top instruments.
[0041] An antibacterial, antiviral, or antimicrobial water-based coating composition is discussed herein that addresses the problems associated with addition of active compound(s), in particular, quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such, to a substrate. The premise of the water-based coating composition lies in the ability to functionalize the substrate with a low-dimensional water-based coating composition that includes active compound(s), in addition to coating the surface of the substrate. The active compound(s) can be composition(s) that protect against transmission of infectious diseases from bacteria or viruses, such as quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such. The water-based coating composition can provide protection against transmission of infectious diseases from bacteria/viruses, like disease-causing viruses (e.g., SARS-CoV-2, MERS-CoV, Influenza A, Ebola, and AIDS) and other infectious agents/contagions .
[0042] After drying/curing, the various compounds used for the coating form an effective hydrophobic layer and thus provide resistance against leaching or loss of the active compound(s) from substrates, such as by water through washing, evaporation, or exposure to exterior environments. The water-based coating composition is hydrophobic and is suitable for treating/coating porous substrates, functionalizing porous plastics, layering on tarpaulin, or coating/functionalizing synthetic/organic fibers, such as those used in manufacturing fabric, linens, garments, and masks, fiber materials used for manufacturing air filters (for heating, ventilation, and air conditioning systems (HVAC)), masonry materials, or aquatic structures. As a nonlimiting example, the water-based coating compositions described herein may be used to enhance the virus-/microorganism-carrier filtration efficiency performance of HVAC air-filters without affecting airflow and may be applied using conventional methods including but not limited to spraying or dipping.
[0043] Without wishing to be bound by theory, it is believed that the components of the waterbased coating composition act as a carrier for the active compound(s) preventing transmission of infectious diseases, which enables deposition and penetration of the quaternary ammonium/phosphonium compound(s), sulfonium compound(s), or derivative(s) of such on and into substrate(s). The carrier can include a solution of hydrophobic chemical agent(s) in some embodiments. It is further believed that the active compound(s) (e.g., quaternary ammonium/phosphonium compound(s), or derivative(s) of such) can chemically react with the hydrophobic chemical agent(s) (e.g., formation of a covalent bond) and/or be physically encapsulated in a covalent network provided by the hydrophobic chemical agent(s), thereby preventing leaching or loss of the active compounds.
[0044] The water-based coating composition can also provide an effective, breathable, penetrating, virucidal/bactericidal coating which exhibits broad spectrum virucidal and bactericidal properties via a simple coating process that prevents/reduces premature leaching or loss of active compound(s) to maintain long term inhibition against infectious agents/contagions.
Viral/bacterial resistance/inhibition/deactivation may be achieved via the inclusion of one or more species of active compounds, such as quaternary ammonium/phosphonium compound(s) or tertiary sulfonium compound(s) that are either target- specific or more general in the particular mechanism of action by which they inhibit, deactivate, and/or lyse the infectious agent(s)/contagion(s). In consideration of the diversity in certain families of viral/bacterial species, the specific mechanism of action by which the effectiveness of the protein in spreading the viruses is inhibited. As a nonlimiting example, in coronaviruses, the outer proteins carry out a number of critical steps, which include standard packaging of the viral RNA as well as helping the viral RNA link up with its replicating enzymes. In particular, by disrupting the protein structure on contact with cationic virucidal agents, the coating inhibits the reproducibility and survivability of infectious viral agents/contagions on the protected surface/substrate.
[0045] Embodiments relate to water-based coating compositions and methods for making water-based coating compositions for substrates. In one particular aspect, a hydrophobic waterbased coating composition is capable of inhibiting/reducing the transmission of infectious diseases in the environment. The hydrophobic water-based coating composition can include water, at least one active compound (e.g., quaternary ammonium/phosphonium compounds, tertiary sulfonium compounds, polyionic compounds, metal salts, metal nanoparticles, metal-oxide nanoparticles, reactive oxygen-generating species, N-halamines, and/or biomacromolecules or derivative(s) of such acting as immobilized virucidal/bactericidal agents), at least one graft polymer backbone agent, and at least one non-ionic emulsifying agent. Optionally, the composition may also include one or more base compounds, co-solvents, bonding agents, plasticizers and other functional additives.
[0046] The water-based coating composition is capable of depositing the active compound(s) not only to the surfaces of the substrate, but also soaking, penetrating, or permeating into internal portions of the substrate (e.g., such that the active compound(s) renders the entirety of the substrate active, not merely the surface).
[0047] In some aspects, the active compound(s) of the water-based coating composition are quaternary ammonium/phosphonium compound(s) or derivative(s) of such that can include a quaternary ammonium/phosphonium cation, which includes a positively charged polyatomic ion with the structure
(QR4)+ where Q is either a nitrogen or phosphorous atom and R is an aryl, alkyl, phenyl, benzyl, allyl, alkenyl, or alkynyl group, and the ammonium/phosphonium cations are permanently charged regardless of the pH environment in which they exist.
[0048] In some aspects, silyl ether, alkoxy silyl, hydroxysilyl, and silyl halide quaternary ammonium/phosphonium silanes can have a general formula of:
Figure imgf000018_0001
where Q is either a nitrogen atom or phosphorous atom, R1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen. [0049] In some aspects, silyl ether, trialkoxysilyl, trihydroxysilyl quaternary ammonium/phosphonium compounds can have a general formula of:
Figure imgf000019_0001
where Q is either a nitrogen atom or phosphorous atom, R1 is a hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen.
[0050] Examples of quaternary ammonium organosilanes used may include but are not limited to: DIMETHYLOCTADECYL[(3-TRIHYDROXYSILYL)PROPYL] AMMONIUM
CHLORIDE (CAS#: 199111-50-7) DIMETHYLOCT ADECYL[(3-
TRIMETHOXYSILYL) PROPYL] AMMONIUM CHLORIDE (CAS#: 27668-52-6), 3- (TRIMETHOXYSILYL)PROPYL-N,N,N-TRIMETHYLAMMONIUM CHLORIDE (CAS#: 35141-36-7), TETRADECYLDIMETHYL(3-TRIMETHOXYSILYLPROPYL)AMMONIUM CHLORIDE, N,N-DIDECYL-N-METHYL-N-(3-TRIMETHOXYSILYLPROPYL)
AMMONIUM CHLORIDE (CAS#: 68959-20-6), OCTADECYLBIS
(TRIETHOXYSILYLPROPYL) AMMONIUM CHLORIDE, 3-(N-STYRYLMETHYL-2- AMINOETHYLAMINO)PROPYLTRIMETHOXYSILANE HYDROCHLORIDE (CAS#: 34937-00-3), S- (TRIMETHOXYSILYLPROPYL) ISOTHIOURONIUM CHLORIDE (CAS#: 84682-36-0), N-(2-N-BENZYLAMINOETHYL)-3-AMINOPROPYLTRIMETHOXYSILANE HYDROCHLORIDE (CAS#: 623938-90-9), TETRADECYLDIMETHYL(3-
TRIMETHOXYSILYLPROPYL) AMMONIUM CHLORIDE (CAS#: 41591-87-1) and 4- (TRIMETHOXYSILYLETHYL)BENZYLTRIMETHYL AMMONIUM CHLORIDE.
[0051] As a nonlimiting example, the quaternary phosphonium organosilanes described and utilized may be formed via reaction of a nucleophilic phosphine-functional compound (e.g., TRIPHENYLPHOSPHINE (CAS#: 603-35-0), DICYCLOHEXYL[2,4,6-TRIS(1- METHYLETHYL)PHENYL]PHOSPHINE (CAS#: 303111-96-9)) with an electrophilic halogenfunctional organosilane (e.g., 3-CHLOROPROPYLTRIMETHOXYSILANE (CAS#: 2530-87-2), ((CHLOROMETHYL) PHENYLETHYL) TRIMETHOXYSILANE (CAS#: 68128-25-6)) via SN2-type nucleophilic substitution to form a quaternary phosphonium organosilane with a cationic phosphonium group stabilized with the anionic halogen leaving group from the halogen-functional organosilane.
[0052] As another nonlimiting example, the quaternary phosphonium organosilanes described and utilized may be formed via reaction of a nucleophilic phosphine-functional organosilane (e.g. 2-(DIPHENYLPHOSPHINO) ETHYLTRIETHXOYSILANE (CAS#: 18586-39-5), 3- (DIPHENYLPHOSPHINO) PROPYLTRIETHOXYSILANE (CAS#: 52090-23-0) VINYL (DIPHENYLPHOSPHINOETHYL)DIMETHYLSILANE (CAS#: 76734-22-0)), with an electrophilic alkyl halide (e.g., 1 -CHLOROOCTADECANE (CAS#: 3386-33-2), 1- CHLOROHEXADECANE (CAS#: 4860-03-1), CHLOROMETHANE (CAS#: 74-87-3)) to form a quaternary phosphonium organosilane with a cationic phosphonium group stabilized with the anionic halogen leaving group from the alkyl halide. [0053] In some embodiments, the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents. In non-limiting embodiments, for example, the concentration of the quaternary ammonium/phosphonium organosilanes in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%,
0.0008%, 0.0009%, 0.0010%, 0.0011%, 0.0012%, 0.0013%, 0.0014%, 0.0015%, 0.0016%,
0.0017%, 0.0018%, 0.0019%, 0.0020%, 0.0021%, 0.0022%, 0.0023%, 0.0024%, 0.0025%,
0.0026%, 0.0027%, 0.0028%, 0.0029%, 0.0030%, 0.0031%, 0.0032%, 0.0033%, 0.0034%,
0.0035%, 0.0036%, 0.0037%, 0.0038%, 0.0039%, 0.0040%, 0.0041%, 0.0042%, 0.0043%,
0.0044%, 0.0045%, 0.0046%, 0.0047%, 0.0048%, 0.0049%, 0.0050%, 0.0051%, 0.0052%,
0.0053%, 0.0054%, 0.0055%, 0.0056%, 0.0057%, 0.0058%, 0.0059%, 0.0060%, 0.0061%,
0.0062%, 0.0063%, 0.0064%, 0.0065%, 0.0066%, 0.0067%, 0.0068%, 0.0069%, 0.0070%,
0.0071%, 0.0072%, 0.0073%, 0.0074%, 0.0075%, 0.0076%, 0.0077%, 0.0078%, 0.0079%,
0.0080%, 0.0081%, 0.0082%, 0.0083%, 0.0084%, 0.0085%, 0.0086%, 0.0087%, 0.0088%,
0.0089%, 0.0090%, 0.0091%, 0.0092%, 0.0093%, 0.0094%, 0.0095%, 0.0096%, 0.0097%,
0.0098%, 0.0099%, 0.0100%, 0.0200%, 0.0250%, 0.0275%, 0.0300%, 0.0325%, 0.0350%,
0.0375%, 0.0400%, 0.0425%, 0.0450%, 0.0475%, 0.0500%, 0.0525%, 0.0550%, 0.0575%,
0.0600%, 0.0625%, 0.0650%, 0.0675%, 0.0700%, 0.0725%, 0.0750%, 0.0775%, 0.0800%,
0.0825%, 0.0850%, 0.0875%, 0.0900%, 0.0925%, 0.0950%, 0.0975%, 0.1000%, 0.1250%,
0.1500%, 0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%,
0.3750%, 0.4000%, 0.4250%, 0.4500%, 0.4750%, 0.5000%, 0.5250%, 0.0550%, 0.5750%,
0.6000%, 0.6250%, 0.6500%, 0.6750%, 0.7000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%,
0.8250%, 0.8500%, 0.8750%, 0.9000%, 0.9250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,
2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%,
4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%,
5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%,
7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%,
8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of at least one of the quaternary ammonium/phosphonium organosilanes mentioned throughout the specification and claims. In non-limiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition. Typically, the concentration of the active compound(s) in the water-based coating composition is between 0.1 and 10 vol. %.
[0054] In some aspects, the active compound(s) of the water-based coating composition are tertiary sulfonium compound(s) or derivative(s) of such that can include a tertiary sulfonium cation, which includes a positively charged polyatomic ion with the structure
(SR3)+ where R is an aryl, alkyl, phenyl, benzyl, allyl, alkenyl, or alkynyl group, and the sulfonium cations are permanently charged regardless of the pH environment in which they exist.
[0055] In some aspects, silyl ether, alkoxy silyl, hydroxysilyl, and silyl halide tertiary sulfonium compounds can have a general formula of:
Figure imgf000023_0001
where R1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen.
[0056] In some aspects, silyl ether, trialkoxysilyl, and trihydroxysilyl tertiary sulfonium compounds can have a general formula of:
Figure imgf000023_0002
where R1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen. [0057] An example of a commercially available tertiary sulfonium organosilane described and used may include but is not limited to: S-(TRIMETHOXYSILYLPROPYL)ISOTHIOURONIUM CHLORIDE (CAS#: 84682-36-0).
[0058] As a nonlimiting example, the tertiary sulfonium organosilanes described and utilized may be formed via reaction of a nucleophilic thioether/sulfide-functional compound (e.g., POLY(1,4-PHENYLENE SULFIDE) (CAS#: 25212-74-2)) with an electrophilic halogenfunctional organosilane (e.g., 3-CHLOROPROPYLTRIMETHOXYSILANE (CAS#: 2530-87-2), ((CHLOROMETHYL) PHENYLETHYL) TRIMETHOXYSILANE (CAS#: 68128-25-6)) via SN2-type nucleophilic substitution to form a tertiary sulfonium organosilane with a cationic sulfonium group stabilized with the anionic halogen leaving group from the halogen-functional organosilane.
[0059] As another nonlimiting example, the tertiary sulfonium organosilanes described and utilized may be formed via reaction of a nucleophilic sulfide-functional organosilane (e.g., BIS[m- (2-TRIETHOXYSILYLETHYL)TOLYL]POLYSULFIDE (CAS#: 198087-81-9/85912-75- 0/67873-85-2), BIS [TRIETHOXYSIL YL)PROPYL]TETRASULFIDE (CAS#: 40372-72-3), 3- MERCAPTOPROPYLTRIMETHOXYSILANE (CAS#: 4420-74-0)) with an electrophilic alkyl halide (e.g., 1 -CHLOROOCTADECANE (CAS#: 3386-33-2), 1 -CHLOROHEXADECANE (CAS#: 4860-03-1), CHLOROMETHANE (CAS#: 74-87-3)) to form a tertiary sulfonium organosilane with a cationic sulfonium group stabilized with the anionic halogen leaving group from the alkyl halide.
[0060] In some embodiments, the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents. In non-limiting embodiments, for example, the concentration of the tertiary sulfonium organosilanes in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about
0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%, 0.0009%,
0.0010%, 0.0011%, 0.0012%, 0.0013%, 0.0014%, 0.0015%, 0.0016%, 0.0017%, 0.0018%,
0.0019%, 0.0020%, 0.0021%, 0.0022%, 0.0023%, 0.0024%, 0.0025%, 0.0026%, 0.0027%,
0.0028%, 0.0029%, 0.0030%, 0.0031%, 0.0032%, 0.0033%, 0.0034%, 0.0035%, 0.0036%
0.0037%, 0.0038%, 0.0039%, 0.0040%, 0.0041%, 0.0042%, 0.0043%, 0.0044%, 0.0045%
0.0046%, 0.0047%, 0.0048%, 0.0049%, 0.0050%, 0.0051%, 0.0052%, 0.0053%, 0.0054%
0.0055%, 0.0056%, 0.0057%, 0.0058%, 0.0059%, 0.0060%, 0.0061%, 0.0062%, 0.0063%
0.0064%, 0.0065%, 0.0066%, 0.0067%, 0.0068%, 0.0069%, 0.0070%, 0.0071%, 0.0072%
0.0073%, 0.0074%, 0.0075%, 0.0076%, 0.0077%, 0.0078%, 0.0079%, 0.0080%, 0.0081%
0.0082%, 0.0083%, 0.0084%, 0.0085%, 0.0086%, 0.0087%, 0.0088%, 0.0089%, 0.0090%
0.0091%, 0.0092%, 0.0093%, 0.0094%, 0.0095%, 0.0096%, 0.0097%, 0.0098%, 0.0099%
0.0100%, 0.0200%, 0.0250%, 0.0275%, 0.0300%, 0.0325%, 0.0350%, 0.0375%, 0.0400%
0.0425%, 0.0450%, 0.0475%, 0.0500%, 0.0525%, 0.0550%, 0.0575%, 0.0600%, 0.0625%
0.0650%, 0.0675%, 0.0700%, 0.0725%, 0.0750%, 0.0775%, 0.0800%, 0.0825%, 0.0850%
0.0875%, 0.0900%, 0.0925%, 0.0950%, 0.0975%, 0.1000%, 0.1250%, 0.1500%, 0.1750%
0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%, 0.3750%, 0.4000%
0.4250%, 0.4500%, 0.4750%, 0.5000%, 0.5250%, 0.0550%, 0.5750%, 0.6000%, 0.6250%
0.6500%, 0.6750%, 0.7000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%, 0.8250%, 0.8500%
0.8750%, 0.9000%, 0.9250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of at least one of the tertiary sulfonium organosilanes mentioned throughout the specification and claims. In non-limiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition. Typically, the concentration of the active compound(s) in the water-based coating composition is between 0.1 and 10 vol. %.
[0061] In general, quaternary ammonium/phosphonium and tertiary sulfonium organosilanes are alkoxy-, hydroxyl-, or halide-functional organosilanes with a quaternary amine/phosphine- functional or sulfonium-functional linear/branched alkyl chain. These compounds are known to exhibit antimicrobial/bactericidal/virucidal properties that can be effectively implemented in biocidal systems, which include but are not limited to microbicides, virucides, bactericides, fungicides, and algaecides. In effect, the hydrolysable alkoxy, hydroxyl, or halide moieties of a quaternary ammonium/phosphonium or tertiary sulfonium organosilane may undergo condensation reactions with silanol, hydroxyl, or halogen moieties of a polymeric host matrix and/or with other quaternary ammonium/phosphonium and/or tertiary sulfonium organosilane compounds in either the presence or absence of a catalyst. The antimicrobial properties of quaternary ammonium/phosphonium and tertiary sulfonium organosilanes arise from positively charged ammonium/phosphonium/sulfonium moieties that exhibit an affinity for the anionic heads of phospholipids that function as critical bilayer-forming components of most cellular membranes or outer protein envelopes/capsids of infectious agents like viruses. The proximity between such ammonium/phosphonium moieties and the lipid bilayers of cellular membranes is enhanced by quaternary ammonium/phosphonium and tertiary sulfonium silanes with longer alkyl chain moieties that facilitate and amplify weak intermolecular attraction between the two. This ionic interaction effectively disrupts protein- spike/outer protein envelope/capsid functionality in infectious agents and cellular activity in prokaryotes via gradual dissociation of cellular membrane lipid bilayers (lysis), which eventually results in rupturing of affected cellular/capsid membranes, leakage of cellular/capsid contents, and ultimately cellular/virionic inactivation.
[0062] In some aspects, the active compound(s) of the water-based coating composition are polymers and/or derivatives of polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyethylacrylic acid (PEAA), polypropylacrylic acid (PPAA), polyvinylbenzoic acid (PVBA), or a copolymer of any combination of above monomers (acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid and vinylbenzoic acid), said polymers having an average molecular weight from 25,000 to 1,000,000 Da.
[0063] In some embodiments, the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents. In non-limiting embodiments, for example, the concentration of the polymers in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%,
0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%, 0.0009%, 0.0010%, 0.0011%,
0.0012%, 0.0013%, 0.0014%, 0.0015%, 0.0016%, 0.0017%, 0.0018%, 0.0019%, 0.0020%,
0.0021%, 0.0022%, 0.0023%, 0.0024%, 0.0025%, 0.0026%, 0.0027%, 0.0028%, 0.0029%,
0.0030%, 0.0031%, 0.0032%, 0.0033%, 0.0034%, 0.0035%, 0.0036%, 0.0037%, 0.0038%, 039%, 0.0040%, 0.0041%, 0.0042%, 0.0043%, 0.0044%, 0.0045%, 0.0046%, 0.0047%,048%, 0.0049%, 0.0050%, 0.0051%, 0.0052%, 0.0053%, 0.0054%, 0.0055%, 0.0056%,057%, 0.0058%, 0.0059%, 0.0060%, 0.0061%, 0.0062%, 0.0063%, 0.0064%, 0.0065%,066%, 0.0067%, 0.0068%, 0.0069%, 0.0070%, 0.0071%, 0.0072%, 0.0073%, 0.0074%,075%, 0.0076%, 0.0077%, 0.0078%, 0.0079%, 0.0080%, 0.0081%, 0.0082%, 0.0083%,084%, 0.0085%, 0.0086%, 0.0087%, 0.0088%, 0.0089%, 0.0090%, 0.0091%, 0.0092%,093%, 0.0094%, 0.0095%, 0.0096%, 0.0097%, 0.0098%, 0.0099%, 0.0100%, 0.0200%250%, 0.0275%, 0.0300%, 0.0325%, 0.0350%, 0.0375%, 0.0400%, 0.0425%, 0.0450%475%, 0.0500%, 0.0525%, 0.0550%, 0.0575%, 0.0600%, 0.0625%, 0.0650%, 0.0675%700%, 0.0725%, 0.0750%, 0.0775%, 0.0800%, 0.0825%, 0.0850%, 0.0875%, 0.0900%925%, 0.0950%, 0.0975%, 0.1000%, 0.1250%, 0.1500%, 0.1750%, 0.2000%, 0.2250%500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%, 0.3750%, 0.4000%, 0.4250%, 0.4500%750%, 0.5000%, 0.5250%, 0.0550%, 0.5750%, 0.6000%, 0.6250%, 0.6500%, 0.6750%000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%, 0.8250%, 0.8500%, 0.8750%, 0.9000%250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%,%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%,%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%,%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%,%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%,%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%,%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%,%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%,%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of at least one of the polymers mentioned throughout the specification and claims. In non-limiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition. Typically, the concentration of the active compound(s) in the water-based coating composition is between 0.1 and 10 vol. %.
[0064] Depending on the pH value of the water-based coating composition, the polymers may exist in full or partially anionic forms with alkali metal counter ions (preferably sodium or potassium). Compared to other related polyanions, PAA and PMAA were found to have antiviral properties in tissue culture and are less cytotoxic. In vitro study showed that PAA and PMAA inhibited the adsorption of the virus to the host cell and suppressed the one-cycle viral synthesis in tissue cultures inoculated with infectious RNA (De Somer et al. J. Virol. 1968, 2, 878-885). In vivo study showed that the broad antiviral action of PAA and PMAA was attributed both to a direct interference with the virus-cell interaction and the viral ribonucleic acid metabolism and to the formation of an interferon-like factor (De Somer et al. J. Virol. 1968, 2, 886-893). Study also showed that combination of anion charge and hydrophobicity of the polymer backbone assists in making up effective broadly acting antiviral polymers (Schandock et al. Adv. Healthcare Mater. 2017, 6, 1700748).
[0065] In some aspects, the tagging agent(s) of the breathable, waterborne, virucidal/bactericidal coating compositions may include copper nanoclusters capped by a silane, which can be used to determine the presence of the infectious virions. The copper nanoclusters capped by a silane exhibit a chromatic shift in the presence of the virus as associated chelating effects activate the copper under UV irradiation. Such a scheme provides a way to not only disrupt viral transmission but also serves as a means to detect the presence of the virus using fluorescence spectroscopy or confocal fluorescence microscopy techniques.
[0066] Alternatively, charged multiblock polymers may be used, wherein the midblock is selectively sulfonated, and therefore hydrophilic. Midblock sulfonation is attributed to a dramatic reduction in surface pH level, and this leads to gram negative results when bacteria accumulate in the lungs due to COVID-19-related infections. The polymers can be used as markers to detect using UV irradiation and fluorescence microscopy the presence of bacteria caused by the presence of COVID-19 and potentially the virus itself.
[0067] In some embodiments, the water-based coating composition for treating the surface of materials may also include graft polymer backbone agent(s). In some embodiments, the graft polymer backbone agent(s) may be hydrophobic and may have a general formula of alkoxyalkylsilane
[CH3(CH2)a]bSiR7c[alkoxy]d where [alkoxy] comprises methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or a combination thereof; R7 comprises a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, or derivatives thereof, and a is an integer from 0 to 20, b is the integer 1, 2, or 3, c is the integer 0, 1, 2, or 3, and d is the integer 1, 2, or 3, provided that the sum of b, c, and d equals 4.
[0068] The preferred alkoxyalkylsilane species may include, but are not limited to, trimethoxyisobutylsilane, triethoxyisobutylsilane, dimethoxydiisobutylsilane, diethoxydiisobutylsilane, trimethoxy(hexyl)silane, triethoxy(hexyl)silane, tripropoxy(hexyl) silane, triisopropoxy(hexyl) silane, trimethoxy(octyl)silane, triethoxy(octyl)silane, tripropoxy(octyl)silane, triisopropoxy(octyl) silane, trimethoxy(decyl)silane, triethoxy(decyl) silane, tripropoxy(decyl)silane, triisopropoxy(decyl)silane, trimethoxy(dodecyl) silane, triethoxy(dodecyl)silane, tripropoxy(dodecyl) silane, triisopropoxy(dodecyl) silane and derivatives bearing similar structures.
[0069] In some embodiments, the hydrophobic chemical agent(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents. In non-limiting embodiments, for example, the concentration of the hydrophobic graft polymer backbone agent(s) having a general formula of alkoxy alkyl silane in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%,
0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%, 0.0009%, 0.0010%, 0.0011%,
0.0012%, 0.0013%, 0.0014%, 0.0015%, 0.0016%, 0.0017%, 0.0018%, 0.0019%, 0.0020%,
0.0021%, 0.0022%, 0.0023%, 0.0024%, 0.0025%, 0.0026%, 0.0027%, 0.0028%, 0.0029%,
0.0030%, 0.0031%, 0.0032%, 0.0033%, 0.0034%, 0.0035%, 0.0036%, 0.0037%, 0.0038%,
0.0039%, 0.0040%, 0.0041%, 0.0042%, 0.0043%, 0.0044%, 0.0045%, 0.0046%, 0.0047%,
0.0048%, 0.0049%, 0.0050%, 0.0051%, 0.0052%, 0.0053%, 0.0054%, 0.0055%, 0.0056%,
0.0057%, 0.0058%, 0.0059%, 0.0060%, 0.0061%, 0.0062%, 0.0063%, 0.0064%, 0.0065%,
0.0066%, 0.0067%, 0.0068%, 0.0069%, 0.0070%, 0.0071%, 0.0072%, 0.0073%, 0.0074%,
0.0075%, 0.0076%, 0.0077%, 0.0078%, 0.0079%, 0.0080%, 0.0081%, 0.0082%, 0.0083%,
0.0084%, 0.0085%, 0.0086%, 0.0087%, 0.0088%, 0.0089%, 0.0090%, 0.0091%, 0.0092%,
0.0093%, 0.0094%, 0.0095%, 0.0096%, 0.0097%, 0.0098%, 0.0099%, 0.0100%, 0.0200%,
0.0250%, 0.0275%, 0.0300%, 0.0325%, 0.0350%, 0.0375%, 0.0400%, 0.0425%, 0.0450%,
0.0475%, 0.0500%, 0.0525%, 0.0550%, 0.0575%, 0.0600%, 0.0625%, 0.0650%, 0.0675%,
0.0700%, 0.0725%, 0.0750%, 0.0775%, 0.0800%, 0.0825%, 0.0850%, 0.0875%, 0.0900%, 0.0925%, 0.0950%, 0.0975%, 0.1000%, 0.1250%, 0.1500%, 0.1750%, 0.2000%, 0.2250%
0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%, 0.3750%, 0.4000%, 0.4250%, 0.4500%
0.4750%, 0.5000%, 0.5250%, 0.0550%, 0.5750%, 0.6000%, 0.6250%, 0.6500%, 0.6750%
0.7000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%, 0.8250%, 0.8500%, 0.8750%, 0.9000%
0.9250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%,
3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%,
5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%,
6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%,
8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%,
9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of at least one of the hydrophobic graft polymer backbone agent(s) having a general formula of alkoxyalkylsilane mentioned throughout the specification and claims. In non-limiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition. Typically, the concentration of the graft polymer backbone agent(s) in the coating composition is between 0.1 and 15 vol. %.
[0070] In some embodiments, the water-based coating composition for treating the surface of materials may also include graft polymer backbone agent(s). In some embodiments graft polymer backbone agent(s) may comprise at least one functional silicone/siloxane in oligomer/co -oligomer form, polymer/co-polymer form, or a combination thereof having a nonlimiting generalized formula of:
Figure imgf000033_0001
with an average molecular weight between 100 to 100,000 Da and an average viscosity between 10 to 20,000 mPa- s, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives/combinations thereof, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh may be the same or dissimilar. X and X’ are an alkoxy group, hydroxyl group, halogen, hydrogen, vinyl group, mercapto/thiol group, amine group, epoxide group, unsubstituted/substituted alkene group, unsubstituted/substituted alkyne group, unsubstituted/substituted allyl group, unsubstituted/substituted alkynyl group, unsubstituted/substituted alkenyl group, an unsubstituted/substituted alkyl group, or a combination thereof, where X and X’ may be the same or dissimilar, z and j are integer values between 1-200,000, where z and j may or may not be equal to one another.
[0071] Such preferred functional silicone/siloxane species may include but are not limited to, VINYL-TERMINATED DIPHENYLSILOXANE COPOLYMER (CAS#: 68951-96-2), VINYL- TERMINATED POLYDIMETHYLSILOXANES (CAS#: 68083-19-2),
VINYLMETHYLSILOXANE-DIMETHYLSILOXANE COPOLYMER, TRIMETHYLS ILOXY-TERMINATED (CAS#: 67762-94-1), HYDRIDE-TERMINATED
POLYDIMETHYLSILOXANE (CAS#: 70900-21-9), METHYLHYDROSILOXANE¬
DIMETHYLSILOXANE COPOLYMER, TRIMETHYLS ILOXY-TERMINATED (CAS#: 68037-59-2), METHYLHYDROSILOXANE-PHENYLMETHYLSILOXANE COPOLYMER,
HYDRIDE-TERMINATED (CAS#: 115487-49-5), SILANOL- TERMINATED
POLYDIMETHYLSILOXANE (CAS#: 70131-67-8), SILANOL- TERMINATED
DIPHENYLSILOXANE (CAS#: 63148-59-4), SILANOL- TERMINATED
POLYTRIFLUOROPROPYLMETHYLSILOXANE (CAS#: 68607-77-2), AMINOPROPYL-
TERMINATED POLYDIMETHYLSILOXANE (CAS#: 106214-84-0), N-
ETHYLAMINOISOBUTYL- TERMINATED POLYDIMETHYLSILOXANE (CAS#: 254891-
17-3), AMINOPROPYLMETHYLSILOXANE-DIMETHYLSILOXANE COPOLYMER
(CAS#: 99363-37-8), AMINOETHYLAMINOPROPYLMETHYLSILOXANE-
DIMETHLSILOXANE COPOLYMER (CAS#: 71750-79-3),
AMINOETHYLAMINOPROPYLMETHOXYSILANE-DIMETHYLSILOXANE
COPOLYMER (CAS#: 67923-07-3), EPOXYPROPOXYPROPYL-TERMINATED
POLYDIMETHYLSILOXANE (CAS#: 102782-97-8),
EPOXYPROPOXYPROPYLMETHYLSILOXANE-DIMETHYLSILOXANE COPOLYMER
(CAS#: 68440-71-7), EPOXYCYCLOHEXYLETHYLMETHYLSILOXANE¬
DIMETHYLSILOXANE COPOLYMER (CAS#: 67762-95-2), CARBINOL- TERMINATED
POLYDIMETHYLSILOXANE (CAS#: 104780-66-7/68937-54-2/161755-53-9),
EPOXYCYCLO HEXYLETHYLMETHYLS ILOXANE-METHOXY-
POLYALKYLENEOXYMETHYLSILOXANE-DIMETHYLSILOXANE TERPOLYMER
(CAS#: 69669-36-9), MONOCARB INOL-TERMINATED POLYDIMETHYLSILOXANE (CAS#: 207308-30-3), MONODICARB INOL-TERMINATED POLYDIMETHYLSILOXANE (CAS#: 218131-11-4), (3-ACRYLOXY-2-HYDROXYPROPOXYPROPYL)-TERMINATED POLYDIMETHYLSILOXANE (CAS#: 128754-61-0), METHACRYLOXYPROPYL- TERMINATED BRANCHED POLYDIMETHYLSILOXANE (CAS#: 80722-63-0), SUCCINIC ANHYDRIDE-TERMINATED POLYDIMETHYLSILOXANE (CAS#: 161208-23-8), (BICYCLOHEPTENYL)ETHYL- TERMINATED POLYDIMETHYLSILOXANE (CAS#: 945244-93-9), CARBOXYALKYL-TERMINATED POLYDIMETHYLSILOXANE (CAS#: 58130-04-4), (CHLOROPROPYL)METHYLSILOXANE-DIMETHYLSILOXANE
COPOLYMER (CAS#: 70900-20-8), CHLOROMETHYL-TERMINATED
POLYDIMETHYLSILOXANE (CAS#: 158465-60-2),
(MERCAPTOPROPYL)METHYLSILOXANE-DIMETHYLSILOXANE COPOLYMER
(CAS#: 102783-03-9), CHLORINE-TERMINATED
NONAFLUOROHEXYLMETHYLSILOXANE-DIMETHYLSILOXANE COPOLYMER
(CAS#: 908858-79-7), MONOCARB INOL-TERMINATED POLYDIMETHYLS ILOXANE- ASSYMETRIC (CAS#: 207308-30-3), MONO(2,3-EPOXY)PROPYLETHER-TERMINATED POLYDIMETHYLSILOXANE (CAS#: 1108731-31-2/127947-26-6), and derivatives of similar/analogous structure.
[0072] In some embodiments, the hydrophobic chemical agent(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents for subsequent reaction(s). In nonlimiting embodiments, for example, the concentration of the graft polymer backbone agent(s) comprising at least one functional silicone/siloxane in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about
0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%, 0.0009%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of at least one of the graft polymer backbone agent(s) comprising at least one functional silicone/siloxane mentioned throughout the specification and claims. In non-limiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition. Typically, the concentration of the hydrophobic chemical agent(s) in the water-based coating composition is between 0.1 and 15 vol. %.
[0073] In some embodiments, the graft polymer backbone agent(s) may be either hydrophobic/hydrophilic and comprise at least one functional silicone/siloxane in oligomer/co- oligomer form, polymer/co-polymer form, or a combination thereof, in combination with a substituted/unsubstituted alkyl functional silyl ether, halogensilane, or silyl hydride having a nonlimiting generalized formula of:
Figure imgf000037_0001
where Ra, Rb, Rc, and Rdare each independent hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, an alkoxy group, a hydroxyl group, a hydrogen atom, or a halogen, where Ra, Rb, and Rc may be the same or dissimilar so long as there exists at least one alkoxy group, hydroxyl group, hydrogen atom, or halogen among Ra, Rb, and Rc. [0074] Such preferred substituted/unsubstituted alkyl-functional silyl ethers, halogensilanes, and silylhydrides include but are not limited to, trimethoxy(hexyl)silane, triethoxy(hexyl)silane, tripropoxy(hexyl) silane, tri-isopropoxy(hexyl)silane, trimethoxy(octyl)silane, triethoxy(octyl)silane, tripropoxy(octyl) silane, tri-isopropoxy(octyl) silane, trimethoxy(decyl) silane, triethoxy(decyl) silane, tripropoxy (decyl) silane, tri-isopropoxy(decyl)silane, trimethoxy(dodecyl)silane, triethoxy(dodecyl) silane, tripropoxy(dodecyl) silane, tri-iso propoxy(dodecyl) silane, and derivatives bearing similar structures.
[0075] In some embodiments, the hydrophobic chemical agent(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents for subsequent reaction(s). In nonlimiting embodiments, for example, the concentration of the graft polymer backbone agent(s) comprising at least one functional silicone/siloxane in combination with a substituted/unsubstituted alkyl functional silyl ether, halogensilane, or silyl hydride in the waterbased coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%,
0.0008%, 0.0009%, 0.0010%, 0.0011%, 0.0012%, 0.0013%, 0.0014%, 0.0015%, 0.0016%,
0.0017%, 0.0018%, 0.0019%, 0.0020%, 0.0021%, 0.0022%, 0.0023%, 0.0024%, 0.0025%,
0.0026%, 0.0027%, 0.0028%, 0.0029%, 0.0030%, 0.0031%, 0.0032%, 0.0033%, 0.0034%,
0.0035%, 0.0036%, 0.0037%, 0.0038%, 0.0039%, 0.0040%, 0.0041%, 0.0042%, 0.0043%,
0.0044%, 0.0045%, 0.0046%, 0.0047%, 0.0048%, 0.0049%, 0.0050%, 0.0051%, 0.0052%,
0.0053%, 0.0054%, 0.0055%, 0.0056%, 0.0057%, 0.0058%, 0.0059%, 0.0060%, 0.0061%,
0.0062%, 0.0063%, 0.0064%, 0.0065%, 0.0066%, 0.0067%, 0.0068%, 0.0069%, 0.0070%,
0.0071%, 0.0072%, 0.0073%, 0.0074%, 0.0075%, 0.0076%, 0.0077%, 0.0078%, 0.0079%,
0.0080%, 0.0081%, 0.0082%, 0.0083%, 0.0084%, 0.0085%, 0.0086%, 0.0087%, 0.0088%, 0.0089%, 0.0090%, 0.0091%, 0.0092%, 0.0093%, 0.0094%, 0.0095%, 0.0096%, 0.0097%
0.0098%, 0.0099%, 0.0100%, 0.0200%, 0.0250%, 0.0275%, 0.0300%, 0.0325%, 0.0350%
0.0375%, 0.0400%, 0.0425%, 0.0450%, 0.0475%, 0.0500%, 0.0525%, 0.0550%, 0.0575%
0.0600%, 0.0625%, 0.0650%, 0.0675%, 0.0700%, 0.0725%, 0.0750%, 0.0775%, 0.0800%
0.0825%, 0.0850%, 0.0875%, 0.0900%, 0.0925%, 0.0950%, 0.0975%, 0.1000%, 0.1250%
0.1500%, 0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%
0.3750%, 0.4000%, 0.4250%, 0.4500%, 0.4750%, 0.5000%, 0.5250%, 0.0550%, 0.5750%
0.6000%, 0.6250%, 0.6500%, 0.6750%, 0.7000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%
0.8250%, 0.8500%, 0.8750%, 0.9000%, 0.9250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,
2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%,
4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%,
5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%,
7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%,
8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of at least one of the graft polymer backbone agent(s) comprising at least one functional silicone/siloxane in combination with a substituted/unsubstituted alkyl functional silyl ether, halogensilane, or silyl hydride mentioned throughout the specification and claims. In nonlimiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition. Typically, the concentration of the hydrophobic chemical agent(s) in the water-based coating composition is between 0.1 and 15 vol. %.
[0076] In some embodiments, the water-based coating composition for treating the surface of materials may also include emulsifying agent(s). The emulsifying agent(s) may include one or more nonionic surfactants, including the use of other chemical agents either alone or in conjunction with nonionic surfactants to perform similar tasks as emulsifying agents. In some embodiments, the nonionic emulsifying agent comprises at least one, preferably ethoxylated, nonionic amphiphilic compound in monomeric form, oligomeric/co -oligomeric form, polymeric/co- polymeric form, or a combination thereof having nonlimiting generalized formulas:
Figure imgf000040_0001
where E is either a hydrocarbon moiety having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or ethoxylates/derivatives/combinations thereof, z, j, and k are integer values between 1- 200, where z, j, and k may or may not be equal to one another. In some embodiments, other chemical agents may be nonionic ethoxylated/alkoxylated fatty acids, ethoxylated alcohols, secondary ethoxylated alcohols, ethoxylated amines, alkyl and nonyl-phenol ethoxylates, ethoxylated sorbitan esters, polysorbates, and ethoxylated oils.
[0077] The preferred nonionic emulsifying agent species may include, but are not limited nor restricted to, 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, ethoxylated tridecyl alcohols, isodecyl alcohol ethoxylates, linear/branched secondary alcohol (C4-C24) ethoxylates, ethoxylated-propoxylated 2-ethyl hexanol, nonylphenoxy poly(ethyleneoxy)ethanol, branched, sorbitan monopalmitate, polyethylene glycol dodecyl ether, di(propylene glycol)monomethyl ether, ethylene diamine tetrakis(ethoxylate-block-propoxylate) tetrol, 2,4,7,9-tetramethyl-5- decyne-4,7-diol ethoxylate, oc-octadecyl-«)-hydroxy-poly(oxy-l,2-ethanediyl), and a-[(l, 1,3,3- tetramethylbutyl)phenyl] - w-hydroxy-poly/oxy- 1 ,2-ethanediyl).
[0078] In some embodiments, the concentration of the emulsifying agent(s) in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%,
0.0008%, 0.0009%, 0.0010%, 0.0011%, 0.0012%, 0.0013%, 0.0014%, 0.0015%, 0.0016%,
0.0017%, 0.0018%, 0.0019%, 0.0020%, 0.0021%, 0.0022%, 0.0023%, 0.0024%, 0.0025%,
0.0026%, 0.0027%, 0.0028%, 0.0029%, 0.0030%, 0.0031%, 0.0032%, 0.0033%, 0.0034%,
0.0035%, 0.0036%, 0.0037%, 0.0038%, 0.0039%, 0.0040%, 0.0041%, 0.0042%, 0.0043%,
0.0044%, 0.0045%, 0.0046%, 0.0047%, 0.0048%, 0.0049%, 0.0050%, 0.0051%, 0.0052%,
0.0053%, 0.0054%, 0.0055%, 0.0056%, 0.0057%, 0.0058%, 0.0059%, 0.0060%, 0.0061%,
0.0062%, 0.0063%, 0.0064%, 0.0065%, 0.0066%, 0.0067%, 0.0068%, 0.0069%, 0.0070%,
0.0071%, 0.0072%, 0.0073%, 0.0074%, 0.0075%, 0.0076%, 0.0077%, 0.0078%, 0.0079%, 0.0080%, 0.0081%, 0.0082%, 0.0083%, 0.0084%, 0.0085%, 0.0086%, 0.0087%, 0.0088%
0.0089%, 0.0090%, 0.0091%, 0.0092%, 0.0093%, 0.0094%, 0.0095%, 0.0096%, 0.0097%
0.0098%, 0.0099%, 0.0100%, 0.0200%, 0.0250%, 0.0275%, 0.0300%, 0.0325%, 0.0350%
0.0375%, 0.0400%, 0.0425%, 0.0450%, 0.0475%, 0.0500%, 0.0525%, 0.0550%, 0.0575%
0.0600%, 0.0625%, 0.0650%, 0.0675%, 0.0700%, 0.0725%, 0.0750%, 0.0775%, 0.0800%
0.0825%, 0.0850%, 0.0875%, 0.0900%, 0.0925%, 0.0950%, 0.0975%, 0.1000%, 0.1250%
0.1500%, 0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%
0.3750%, 0.4000%, 0.4250%, 0.4500%, 0.4750%, 0.5000%, 0.5250%, 0.0550%, 0.5750%
0.6000%, 0.6250%, 0.6500%, 0.6750%, 0.7000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%
0.8250%, 0.8500%, 0.8750%, 0.9000%, 0.9250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,
2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%,
4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%,
5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%,
7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%,
8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of the emulsifying agent(s) mentioned throughout the specification and claims. In non-limiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition. [0079] In some embodiments, the water-based coating composition for treating the surface of materials may also include solvent(s). In some embodiments, in addition to water, the solvent(s) used to disperse all the components to form a homogeneous solution/emulsion may include, but is not limited to, methanol, ethanol, phenoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol acetone, acetonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, di(propylene glycol) methyl ether, 4-chlorobenzotrifluoride, odorless mineral spirits/petroleum distillates or a mixture/combination thereof.
[0080] In some embodiments, the concentration of the solvent(s) in the water-based coating composition comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%, 0.0006%, 0.0007%, 0.0008%,
0.0009%, 0.0010%, 0.0011%, 0.0012%, 0.0013%, 0.0014%, 0.0015%, 0.0016%, 0.0017%,
0.0018%, 0.0019%, 0.0020%, 0.0021%, 0.0022%, 0.0023%, 0.0024%, 0.0025%, 0.0026%,
0.0027%, 0.0028%, 0.0029%, 0.0030%, 0.0031%, 0.0032%, 0.0033%, 0.0034%, 0.0035%,
0.0036%, 0.0037%, 0.0038%, 0.0039%, 0.0040%, 0.0041%, 0.0042%, 0.0043%, 0.0044%,
0.0045%, 0.0046%, 0.0047%, 0.0048%, 0.0049%, 0.0050%, 0.0051%, 0.0052%, 0.0053%,
0.0054%, 0.0055%, 0.0056%, 0.0057%, 0.0058%, 0.0059%, 0.0060%, 0.0061%, 0.0062%,
0.0063%, 0.0064%, 0.0065%, 0.0066%, 0.0067%, 0.0068%, 0.0069%, 0.0070%, 0.0071%,
0.0072%, 0.0073%, 0.0074%, 0.0075%, 0.0076%, 0.0077%, 0.0078%, 0.0079%, 0.0080%,
0.0081%, 0.0082%, 0.0083%, 0.0084%, 0.0085%, 0.0086%, 0.0087%, 0.0088%, 0.0089%,
0.0090%, 0.0091%, 0.0092%, 0.0093%, 0.0094%, 0.0095%, 0.0096%, 0.0097%, 0.0098%,
0.0099%, 0.0100%, 0.0200%, 0.0250%, 0.0275%, 0.0300%, 0.0325%, 0.0350%, 0.0375%,
0.0400%, 0.0425%, 0.0450%, 0.0475%, 0.0500%, 0.0525%, 0.0550%, 0.0575%, 0.0600%, 0.0625%, 0.0650%, 0.0675%, 0.0700%, 0.0725%, 0.0750%, 0.0775%, 0.0800%, 0.0825%
0.0850%, 0.0875%, 0.0900%, 0.0925%, 0.0950%, 0.0975%, 0.1000%, 0.1250%, 0.1500%
0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000%, 0.3250%, 0.3500%, 0.3750%
0.4000%, 0.4250%, 0.4500%, 0.4750%, 0.5000%, 0.5250%, 0.0550%, 0.5750%, 0.6000%
0.6250%, 0.6500%, 0.6750%, 0.7000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%, 0.8250%
0.8500%, 0.8750%, 0.9000%, 0.9250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%,
1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%,
3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%,
4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%,
6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4%,
7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%,
9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of the solvent(s) mentioned throughout the specification and claims. In non-limiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
[0081] In some embodiments, the water-based coating composition may optionally include one or more base compounds, bonding agents, plasticizers, chelating agents, and/or other functional additives. In some embodiments, the base compound(s) are a core unit or base of the sol-gel network. In some embodiments, the base compound used has a general formula of M(OR6)4, where M is Si, Al, Ti, In, Sn or Zr; and R6 is a hydrogen, a substituted or unsubstituted alkyl group or a derivative thereof. In a preferred embodiment, the base compound is tetraethyl orthosilicate (Si(OCH2CH3)4).
[0082] In some embodiments, the water-based coating composition may include bonding agent to aid bonding of the coating to the desired surface. In some embodiments, the bonding compound used has a general formula of M(0R7) R R9 Z, where M is Si, Al, In, Sn or Ti; R7 is a hydrogen, a substituted or unsubstituted alkyl group or derivatives thereof; R8 is a hydrogen, a substituted or unsubstituted alkyl group or derivatives thereof; R9 is a substituted or unsubstituted epoxy or glycidoxy group; and x and z are each independent integers from 1 to 3, y is an integer from 0 to 2, and the sum of x, y and z is 4. In the preferred embodiments, the bonding agent is 3- glycidoxypropyltrimethoxysilane (Si(OCH3)3glycidoxy).
[0083] In some embodiments, the water-based coating composition may include a plasticizer to increase or maintain elasticity of the coating to be formed. In some embodiments, the plasticizer used in the water-based coating composition has the general formula of M(OR10)4-I 1 where M is Si, Al, In, Sn or Ti; R10 is a hydrogen, a substituted or unsubstituted alkyl group or derivatives thereof; and R11 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group or a derivative thereof; and x is 1, 2 or 3. In a preferred aspect, the plasticizer is trimethoxypropylsilane (Si(OCH3)3CH2CH2CH3).
[0084] In some embodiments, the water-based coating composition can include a chelating agent to enhance homogeneity of the organic/inorganic compounds or portions of compounds in the solution. In some embodiments, the chelating agent is an alkoxysilane, metal oxide precursor, or both having the general formula of M(0R12)^ R13? R14 z, where M is Si, Al, In, Sn or Ti; R12 includes a hydrogen, a substituted or unsubstituted alkyl group, or derivatives thereof; R13 includes a hydrogen, a substituted or unsubstituted alkyl group, or derivatives thereof; R14 includes a substituted or unsubstituted alky or alkenyl group having from 3 to 20 carbon atoms or a substituted or unsubstituted amine (including primary, secondary and tertiary) or thiol; and x and z are each independently an integer from 1 to 3, y is an integer from 0 to 2, and the sum of x, y, and z is 4.
[0085] In some embodiments, the concentration of the base compounds, bonding agents, plasticizers, chelating agents, and/or other functional additives in the water-based coating composition, individually or in combination, comprises, consists essentially of, or consists of, in their final form, for example, at least about 0.0001%, 0.0002%, 0.0003%, 0.0004%, 0.0005%,
0.0006%, 0.0007%, 0.0008%, 0.0009%, 0.0010%, 0.0011%, 0.0012%, 0.0013%, 0.0014%,
0.0015%, 0.0016%, 0.0017%, 0.0018%, 0.0019%, 0.0020%, 0.0021%, 0.0022%, 0.0023%,
0.0024%, 0.0025%, 0.0026%, 0.0027%, 0.0028%, 0.0029%, 0.0030%, 0.0031%, 0.0032%,
0.0033%, 0.0034%, 0.0035%, 0.0036%, 0.0037%, 0.0038%, 0.0039%, 0.0040%, 0.0041%,
0.0042%, 0.0043%, 0.0044%, 0.0045%, 0.0046%, 0.0047%, 0.0048%, 0.0049%, 0.0050%,
0.0051%, 0.0052%, 0.0053%, 0.0054%, 0.0055%, 0.0056%, 0.0057%, 0.0058%, 0.0059%
0.0060%, 0.0061%, 0.0062%, 0.0063%, 0.0064%, 0.0065%, 0.0066%, 0.0067%, 0.0068%
0.0069%, 0.0070%, 0.0071%, 0.0072%, 0.0073%, 0.0074%, 0.0075%, 0.0076%, 0.0077%
0.0078%, 0.0079%, 0.0080%, 0.0081%, 0.0082%, 0.0083%, 0.0084%, 0.0085%, 0.0086%
0.0087%, 0.0088%, 0.0089%, 0.0090%, 0.0091%, 0.0092%, 0.0093%, 0.0094%, 0.0095%
0.0096%, 0.0097%, 0.0098%, 0.0099%, 0.0100%, 0.0200%, 0.0250%, 0.0275%, 0.0300%
0.0325%, 0.0350%, 0.0375%, 0.0400%, 0.0425%, 0.0450%, 0.0475%, 0.0500%, 0.0525%
0.0550%, 0.0575%, 0.0600%, 0.0625%, 0.0650%, 0.0675%, 0.0700%, 0.0725%, 0.0750%
0.0775%, 0.0800%, 0.0825%, 0.0850%, 0.0875%, 0.0900%, 0.0925%, 0.0950%, 0.0975%
0.1000%, 0.1250%, 0.1500%, 0.1750%, 0.2000%, 0.2250%, 0.2500%, 0.2750%, 0.3000% 0.3250%, 0.3500%, 0.3750%, 0.4000%, 0.4250%, 0.4500%, 0.4750%, 0.5000%, 0.5250%,
0.0550%, 0.5750%, 0.6000%, 0.6250%, 0.6500%, 0.6750%, 0.7000%, 0.7250%, 0.7500%, 0.7750%, 0.8000%, 0.8250%, 0.8500%, 0.8750%, 0.9000%, 0.9250%, 0.9500%, 0.9750%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%,
2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%,
4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%,
5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%,
7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%,
8.6%, 8.7%, 8.8%, 8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%,
11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% or any range derivable therein, of the base compounds, bonding agents, plasticizers, chelating agents, and/or other functional additives mentioned throughout the specification and claims. In nonlimiting aspects, the percentage can be calculated by weight or volume of the total composition. A person of ordinary skill in the art would understand that the concentrations can vary depending on the addition, substitution, and/or subtraction of ingredients in a given composition.
[0086] In some embodiments, the waterborne virucidal/bactericidal coating composition can be prepared by: (a) obtaining at least one active compound, at least one graft polymer backbone agent, and at least one solvent, and optionally one or more base compound(s), bonding agent(s), plasticizer(s), and/or chelating agent(s); (b) adding the above mentioned ingredients to the solvent(s) to form a solution/mixture; and (c) optionally mixing the solution/mixture with water under acidic conditions (e.g., pH of 6 or less, or pH < 5) to form a homogeneous sol-gel solution. The solution can be stirred at a temperature from 50 to 100 °C for between 10 seconds (fast- reactions) to 10 days (slower reactions). The quaternary ammonium compound(s) or derivative(s) of such are either chemically reacted to the hydrophobic chemical agent(s) to form covalent bonds or physically entrapped/encapsulated with the materials used for the coating.
[0087] In some embodiments, the waterborne virucidal/bactericidal coating composition can be prepared by emulsifying and/or homogenizing an aqueous colloidal suspension of active compound(s), graft polymer backbone agent(s), emulsifying agent(s), and optional hydrophobic agent(s), co-solvent(s), bonding agent(s), plasticizer agent(s), and/or chelating agents using either ultrasonication techniques, or preferably, using a high-pressure homogenizer or high-shear emulsifier (e.g., SIL VERSON® L5M-A). Referring to FIG. 1, shown are some steps of the present methods of preparing the waterborne virucidal/bactericidal coating compositions. The waterborne virucidal/bactericidal coating compositions can be made by a step 10 of mixing at least one cosolvent and at least one graft polymer backbone agent to form a first mixture; a step 14 of adding at least one active compound and at least one emulsifying agent to the first mixture to form a second mixture; a step 18 of adding water to the second mixture to form a third mixture comprising a colloidal suspension; and a step 22 of emulsifying the third mixture. Some methods may also comprise a step 26 of adding to the second mixture a base compound, a bonding agent, a hydrophobing agent, a plasticizer, and/or a chelating agent.
[0088] While using a high-shear/high-pressure emulsifier/homogenizer, mechanical emulsification parameters like rotor frequency, emulsification time, emulsification temperature, applied pressure, and solution volume varies depending on the volume and chemistry of solution to be emulsified relative to the specifications of each high-shear emulsifier/mixer unit, the geometry of the vessel containing the solution to be emulsified, the position of workhead (rotor- stator assembly) in the emulsification vessel, the dynamics of the homogenization pressure chamber, and the specifications of the rotor/stator.
[0089] As a nonlimiting example, smaller volumes of Precursor A of typically less than 1 liter may be bath sonicated at 35 kHz in a sealed borosilicate glass, stainless steel, or hard plastic vessel for 1-2 hours at 38 °C to yield a stable mini-emulsion with sub-500-nm colloids. As another nonlimiting example, a larger volumes of Precursor A may be homogenized in a high-shear batch emulsifier using a compatible high-shear perforated square -/circular-hole stator with a workhead of appropriate dimensions operating at between 5000 - 10,000 RPM and at temperature between 25- 90 °C for 1-5 hours in a cylindrical reaction vessel to yield a stable micro-emulsion with colloids with a mean diameter of < 2000 nm.
[0090] An another nonlimiting examples, a larger volumes of Precursor A may be homogenized/emulsified to yield a stable mini-/nano-emulsion using a suitable high-pressure homogenizer operating at pressures values between 50-200 MPa and at a temperature between 25- 90 °C. It should be noted that each particular high-shear mixing/emulsification system will accordingly require different emulsification parameters to achieve the same desired degree and dispersity of emulsification. Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein. In one aspect, a method of coating a substrate in need of a coating can include (a) obtaining a substrate (e.g., fabrics; porous substrates and tarps, textiles, fiber materials used for manufacturing air filters, masonry materials, or aquatic structures); and (b) applying the waterbased coating composition(s) discussed above or herein to the substrate, wherein the water-based coating composition imparts virucidal/bactericidal/biocidal and water repellent properties to the substrate. Virucidal/bactericidal properties can be imparted to the outside surfaces of the substrate, impregnated in the substrate, or chemically incorporated into the substrate. In some embodiments, the water-based coating composition can be deposited on the surface of substrates by spraying, misting, doctor-blading, padding, foaming, flooding, dipping, rolling, or inkjet printing. In some embodiments, the water-based coating composition is applied by (a) contacting the substrate with a solution comprising the water-based coating composition to coat the substrate; and (b) subjecting the coated material to conditions sufficient to remove the solvents and dry the material, where at least a portion of the water-based coating composition penetrates the surface of the substrate. Thus, referring to FIG. 2, shown are some steps of the present methods of preparing the substrates coated with the waterborne virucidal/bactericidal coating compositions. The waterborne virucidal/bactericidal coated-substrates can be made by a step 30 of coating a substrate with the waterborne virucidal/bactericidal coating compositions; and a step 34 of treating the coated substrate to remove the water and co-solvents and to cure the coated substrate. The conditions of step 14 can include a temperature of 25 to 200 °C and/or can be sufficient to crosslink the sol-gel. In some embodiments, the waterborne virucidal/bactericidal coating composition formed on the substrate does not change the feel and texture of the substrate before coating.
[0091] In some embodiments, certain cellulose semi-permeable membranes, which are used in kidney dialysis, can also be potentially coated with the breathable, waterborne, virucidal/bactericidal coating compositions discussed herein that can act as a filtration device that immobilizes infectious virions/microbes. The coated membrane acts in the dialysis system as a mechanism to both destroy the virus but also remove infectious virions/bacteria from the blood stream. [0092] In some embodiments, a method of inhibiting leaching of active compound(s) (e.g., quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such) from a substrate is disclosed. The method can include applying the waterbased coating composition described throughout the specification and drying the coated substrate. The water-based coating composition inhibits leaching of active compound(s) from the substrate by forming covalent bonds between the hydrophobic chemical agent(s) and the active compound(s) of the water-based coating composition and/or physically entrapping/encapsulating the active compound(s) within the water-based coating composition. In some embodiments, the water-based coating composition described throughout the specification inhibits the leaching of active compound(s) at the efficiency of more than 95%.
[0093] In some embodiments, a method of forming a coating on a substrate comprises the steps of:
(a) selecting a substrate;
(b) treating the substrate with a water-based coating composition to coat the substrate with a viral/bacterial reduction coating, wherein the water-based coating composition comprises water, at least one active compound, hydrophobic chemical agent, and solvent;
(c) subjecting the coated substrate to conditions sufficient to remove the solvents and cure the substrate, such as at a temperature equal to or between 25-200° C, after the treating step to form a cured coating. The water-based coating composition forms an interpenetration polymer network that inhibits leaching of an active compound from the substrate by forming covalent bonds between the hydrophobic chemical agent(s) and the active compound(s) of the water-based coating composition or physically entrapping/encapsulating the active compound(s) within the waterbased coating composition, and the cured coating is flexible. [0094] In some embodiments, the method of any embodiments discussed above may further include at least one active compound that comprises a quaternary ammonium compound or derivative of such capable of destroying infectious agents/contagions, such as enveloped viruses like SARS-CoV (the virus that causes COVID- 19) and Influenza A viruses; and/or capable of destroying bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica and Pseudomonas aeruginosa.
[0095] In some embodiments, the quaternary ammonium compound or derivative of such of any embodiment discussed above comprises of an active cationic species with a general formula of:
(QR4)+ where Q is either a nitrogen or phosphorous atom and R is an aryl or alkyl group.
[0096] In some embodiments, the quaternary ammonium compound of any embodiment discussed above comprises a silyl ether, alkoxysilyl, hydroxysilyl, and silyl halide quaternary ammonium/phosphonium silanes with the generalized nonlimiting formula:
Figure imgf000052_0001
where Q is either a nitrogen atom or phosphorous atom, R1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen.
[0097] Alternatively, the quaternary ammonium compound of any embodiment discussed above comprises silyl ether, trialkoxysilyl, trihydroxysilyl quaternary ammonium/phosphonium compounds with a general nonlimiting formula of:
Figure imgf000053_0001
where Q is either a nitrogen atom or phosphorous atom, R1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen.
[0098] In some embodiments, the method of any embodiments discussed above may further include at least one active compound that comprises a tertiary sulfonium compound or derivative of such capable of destroying infectious agents/contagions, such as enveloped viruses like SARS- CoV (the virus that causes COVID-19) and Influenza A viruses; and/or capable of destroying bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica and Pseudomonas aeruginosa. [0099] In some embodiments, the tertiary sulfonium compound(s) or derivative(s) of such of any embodiment discussed above includes a positively charged polyatomic ion with the structure
(SR3)+ where R is an aryl, alkyl, phenyl, benzyl, allyl, alkenyl, or alkynyl group) and has a generalized formula of:
Figure imgf000054_0001
where R1 is an alkoxy group, hydroxyl group, halogen, hydrogen, or an alkyl group or any combination thereof that includes at least one alkoxy/hydroxyl group; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen.
[00100] Alternatively, silyl ether, trialkoxysilyl, and trihydroxysilyl tertiary sulfonium compounds of any embodiment discussed above can have a general formula of:
Figure imgf000054_0002
where R1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group or a combination thereof; R2, R3, R4, and R5 are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a phenyl group, a benzyl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives thereof, and Z is an anionic atom or compound, preferably a halogen.
[00101] In some embodiments, the method of any embodiments discussed above may further include at least one active compound that comprises a polymer or derivative of such capable of destroying infectious agents/contagions, such as enveloped viruses like SARS-CoV (the virus that causes COVID-19) and Influenza A viruses; and/or capable of destroying bacteria including Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococci, Enterococcus faecalis, Salmonella enterica and Pseudomonas aeruginosa.
[00102] In some embodiments, the polymer or derivative of such of any embodiment discussed above comprises polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly ethylacry lie acid (PEAA), polypropylacrylic acid (PPAA), polyvinylbenzoic acid (PVBA), or a copolymer of any combinations of the above monomers (acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid and vinylbenzoic acid), said polymers having an average molecular weight from 25,000 to 1,000,000 Da. In some embodiments, the active compound(s) may be dissolved or dispersed in an organic solvent or a mixture of organic solvents. Depending on the pH value of the water-based coating composition, the polymers may exist in full or partially anionic forms with alkali metal counter ions (preferably sodium or potassium).
[00103] In some embodiments, the method of any embodiments discussed above may further include a graft polymer backbone agent comprising an alkoxyalkylsilane wherein the alkoxyalkylsilane has a general formula of: [CH3(CH2)a]bSiR7c[alkoxy]d where [alkoxy] comprises methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or a combination thereof; R7 comprises a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, or derivatives thereof, and a is an integer from 0 to 20, b is the integer 1, 2, or 3, c is the integer 0, 1, 2, or 3, and d is the integer 1, 2, or 3, provided that the sum of b. c and d equals 4.
[00104] In some embodiments, the graft polymer backbone agent of any embodiment discussed above comprises at least one functional silicone/siloxane in oligomer/co-oligomer form, polymer/co-polymer form, or a combination thereof having a nonlimiting generalized formula of:
Figure imgf000056_0001
with an average molecular weight between 100 to 100,000 Da and an average viscosity between 10 to 20,000 mPa- s, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are each independently hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, a substituted alkynyl group, an unsubstituted alkynyl group, a substituted aryl group, an unsubstituted aryl group, a substituted allyl group, an unsubstituted allyl group, or derivatives/combinations thereof, where Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh may be the same or dissimilar. X and X’ are an alkoxy group, hydroxyl group, halogen, hydrogen, vinyl group, mercapto/thiol group, amine group, epoxide group, unsubstituted/substituted alkene group, unsubstituted/substituted alkyne group, unsubstituted/substituted allyl group, unsubstituted/substituted alkynyl group, unsubstituted/substituted alkenyl group, an unsubstituted/substituted alkyl group, or a combination thereof, where X and X’ may be the same or dissimilar, z and j are integer values between 1-200,000, where z and j may or may not be equal to one another.
[00105] Alternatively, the graft polymer backbone agent of any embodiment discussed above may include one or more substituted/unsubstituted alkyl-functional silyl ether, halogensilane, or silylhydride of the generalized structure:
Figure imgf000057_0001
where Ra, Rb, Rc, and Rdare each independent hydrocarbon moieties having between 1 to 30 carbon atoms, a methyl group, a phenyl group, a benzyl group, a substituted alkyl group (e.g., aminoalkyl group, mercaptoalkyl group, glycidoxyalkyl group), an unsubstituted alkyl group, a substituted alkenyl group, an unsubstituted alkenyl group, an alkoxy group, a hydroxyl group, a hydrogen atom, or a halogen, where Ra, Rb, and Rc may be the same or dissimilar so long as there exists at least one alkoxy group, hydroxyl group, hydrogen atom, or halogen among Ra, Rb, and Rc.
[00106] In some embodiments, the method of any embodiments discussed above may further include a solvent used to disperse all the components to form a homogeneous solution/emulsion. In addition to water, the solvent may include methanol, ethanol, phenoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol acetone, acetonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, di(propylene glycol)methyl ether, 4- chlorobenzotrifluoride, odorless mineral spirits/petroleum distillates, or a mixture/combination thereof. [00107] In some embodiments, the waterborne virucidal/bactericidal coating composition can be prepared by (a) obtaining at least one active compound, at least one graft polymer backbone agent, and at least one solvent, and optionally, one or more base compound, bonding agent, plasticizer and/or chelating agent; (b) adding the above mentioned ingredients to the solvent(s) to form a solution/mixture; and (c) optionally mixing the solution/mixture with water under acidic conditions (e.g., pH of 6 or less, or pH < 5) to form a homogeneous sol-gel solution. The solution can be stirred at a temperature from 50 to 100 °C for between 10 seconds (fast-reactions) to 10 days (slower reactions). The quaternary ammonium compound(s) or derivative(s) of such are either chemically reacted to the hydrophobic chemical agent(s) to form covalent bonds or physically entrapped/encapsulated with the materials used for the coating.
[00108] In some embodiments, the waterborne virucidal/bactericidal coating composition can be prepared by emulsifying and/or homogenizing an aqueous colloidal suspension of active compound(s), graft polymer backbone agent(s), emulsifying agent(s), and optional hydrophobic agent(s), co-solvent(s), bonding agent(s), plasticizer agent(s), and/or chelating agents using either ultrasonication techniques, or preferably, using a high-pressure homogenizer or high-shear emulsifier.
[00109] In a particular embodiment, a high-shear batch mixer may be used to mechanically emulsify/homogenize the aqueous colloidal suspension of active compound(s), graft polymer backbone agent(s), emulsifying agent(s), and optional hydrophobing agent(s), co-solvent(s), bonding agent(s), plasticizer agent(s), and/or chelating agents by shearing at operating frequencies between 5,000-10,000 RPM and at temperature between 25-90 °C for between 1-5 hours, until the desired mean colloid diameter and dispersity is achieved. Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
[00110] In some embodiments, a method of inhibiting leaching of active compound(s) (e.g., quaternary ammonium/phosphonium compound(s), tertiary sulfonium compound(s), or derivative(s) of such) from a substrate is disclosed. The method can include applying the waterbased coating composition described throughout the specification and drying the coated substrate. The water-based coating composition inhibits leaching of active compound(s) from the substrate by forming covalent bonds between the hydrophobic chemical agent(s) and the active compound(s) of the water-based coating composition and/or physically entrapping/encapsulating the active compound(s) within the water-based coating composition. In some embodiments, the water-based coating composition described throughout the specification inhibits the leaching of active compound(s) at the efficiency of more than 95%.
[00111] In some embodiments, the method of any embodiments discussed above includes substrates that are functionalizing porous plastics, tarpaulin, synthetic/organic fibers such as those used in manufacturing fabric, linens, garments, and mask, fiber materials used for manufacturing air filters (for heating, ventilation, air conditioning, filters for buildings, cars, boats, planes, filtration in dialysis and other biological instruments). Other substrates may also include masonry, concrete, stone, brick, stucco, grout, wood-based products, fences, decks, furniture and porous ornaments or other porous structures. In some embodiments, the waterborne virucidal/bactericidal coating composition formed on the substrate does not change the feel and texture of the substrate before coating. Experimental Procedures and Test Results
[00112] Below are detailed descriptions of the standardized test methods used to evaluate the efficacy of treated samples in regard to aqueous liquid repellency. The treatments were done on specific denier fibers but can vary depending on the number of filaments and size of the denier, and so the AATCC test results may vary. When testing non-woven fibers or other three- dimensional filaments, the length and density may also alter the AATCC results.
[00113] AATCC Test Method 193-2012 (Aqueous Liquid Repellency (ALR): Water/Alcohol Solution Resistance Test). The purpose of this test method is to determine the efficacy of coatings that can reduce the effective surface energy of arbitrary fabric material in regard to the treated surface’s ability to resist wetting by a specific series of water/isopropanol solutions. This test method implements 8 aqueous isopropanol solutions, numbered 1 to 8 of varying volumetric ratios (1 = largest water: i-PrOH volumetric ratio and 8 = smallest water: i-PrOH volumetric ratio), which correspond to different surface energies. The test is conducted by placing a minimum of three 0.050 mL drops of solution, beginning with the lowest numbered test solution, and spaced ~ 4.0 cm apart from one another with the applicator tip held at a height of ~ 0.60 cm above the surface of a flat test specimen. In order to receive a passing grade, the test solution must remain on the surface of the test specimen for 10 ± 2.0 seconds without darkening, wetting, or wicking into the fibers of the test specimen. Correspondingly, the aqueous liquid repellency grade of the test specimen is the highest numbered test solution that receives a passing grade.
[00114] Below are detailed descriptions of the standardized test methods used to evaluate the efficacy of treated samples in regard to the leachability of the active compound(s), specifically the quaternary ammonium compound(s) from fabrics treated with the water-based virucidal/bactericidal coating. [00115] ASTM E 2149-13a: Standard Test Method for Determining the Antimicrobial Activity of Antimicrobial Agents Under Dynamic Contact Conditions. The purpose of this test method is to perform the leaching procedure on fabrics treated with the water-based virucidal/bactericidal coating and obtain leachates that are further analyzed by ASTM D5806-95 (2017). The leaching apparatus is a loose tea-leaf steeper atop a beaker containing deionized water. The cured fabric sample treated with the water-based virucidal/bactericidal coating is neatly folded and placed at the bottom of the apparatus. The cap of the leaching apparatus contains a depressor to ensure the sample remains submerged throughout the leaching process.
[00116] The steps of the leaching procedure are as follows: 1) Carefully place the leaching apparatus on a beaker containing 275 mL deionized water. 2) Set the stirrer/hotplate to 1100 rpm and 35 °C and start the timer for 1 hour. 3) After 1 hour, carefully remove the apparatus and collect the leachate for the leaching experiment. A more aggressive leaching process is also carried out by using 275 mL non-ionic sulfactant MAKON® DA-4 (0.02 v/v %) in deionized water instead.
[00117] ASTM D5806-95 (2017): Standard Test Method for Disinfectant Quaternary Ammonium Salts by Potentiometric Titration. The purpose of this test method is to determine the concentration of the active quaternary ammonium compound in the leachate by titration with sodium lauryl sulfate. All reagents were prepared as prescribed in ASTM D5806-95 (2017). For potentiometric titration, 100 mL analyte (leachate from leaching experiment per ASTM E2149), 10 mL borate buffer solution, 2 mL isopropyl alcohol, and 2 mL 1.0 v/v % MAKON® DA-4 are combined in a 150-mL beaker. The final solution is potentiometrically titrated with 8.39 x 10’3 N sodium lauryl sulfate and the volume of titrant (SLS) used to completely titrate the nitrate ions
(active molecules) present in the analyte is determined. [00118] Quaternary ammonium compound solution of known concentration dissolved in deionized water (ppm or mg/L) is used to determine the volume of titrant (SLS) required to completely titrate the active cations present in the quaternary ammonium compound solution. To determine the active compound concentration in the leachate, the titrant volume is used to titrate the unknown concentration of quaternary ammonium compound in the leachate and correlated with the known titrant volume used for completely titrating the known concentration of quaternary ammonium compound solution. For example, 5 mL SLS was consumed to completely titrate the quaternary ammonium compound solution of known concentration of 200 ppm. If 2.5 mL of SLS is consumed to completely titrate the leachate of unknown quaternary ammonium compound concentration, the concentration of quaternary ammonium compound in the leachate is 100 ppm. [00119] The detection limit in the current experimental setup using a HANNA™ HI931 Automatic Potentiometric Titrator equipped with HI4113 Nitrate Combination electrode is about 10 ppm for all three quaternary ammonium compounds: BENZETHONIUM CHLORIDE (used as the titration standard) (CAS#: 121-54-0), DIMETHYLOCTADECYL[(3- TRIHYDROXYS IL YL) PROPYL] AMMONIUM CHLORIDE (CAS#: 199111-50-7) and DIMETHYLOCTADECYL[(3-TRIMETHOXYSILYL)PROPYL] AMMONIUM CHLORIDE (CAS#: 27668-52-6).
[00120] The following describes a synthesis procedure for waterborne, biocompatible, non- cytotoxic, breathable, virucidal/bactericidal, non-leaching coating compositions that also renders the coated surface permanently hydrophobic and a one-stage wet-chemical treatment process for treating porous fiber materials with said coating compositions: Example I
[00121] A precursor solution of methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane (CAS: 102782-92-3/75718-16-0) (i.e., poly(3-((2- aminoethyl)amino)propyl)methyl(dimethyl)siloxane) in a co-solvent blend of methyl acetate, 4- chlorobenzotrifluoride, and dimethyl carbonate was prepared under stirring (Precursor A). A designated amount of Precursor A was heated to a temperature of 40 °C under stirring. After 5 minutes, specific amounts of bonding agent (3-glycidoxypropyl)trimethoxysilane was added to initiate nucleophilic addition with primary amine groups of the graft polymer backbone agent via an SN2-type epoxide ring-opening mechanism. After 5 minutes, hydrophobing and plasticizer agent n-propyltrimethoxysilane was added followed by designated amounts of nonionic emulsifying agent di(propylene glycol)monomethyl ether. After 2 minutes, specific amounts of active compound octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, bonding agent 3 -chloropropyltrimethoxy silane, and co- solvent methanol were slowly added concomitantly followed by a designated amount of nonionic emulsifying agent isodecyl alcohol ethoxylate (CAS: 78330-20-8). A single-phase, homogeneous, transparent solution was obtained (Precursor B). After 2 minutes, all added de-ionized water was slowly added to Precursor B at a rate of ~ 20 mL/s under vigorous stirring. A white, turbid, macroscale, homogeneous colloidal suspension was immediately obtained with a pH between 5.5 and 7 - no indication of flocculation or aggregation was observed.
[00122] The resulting colloidal suspension (Precursor C) was mechanically emulsified using either ultrasonication techniques, or preferably, using a high-pressure homogenizer or high-shear emulsifier (e.g., Silverson L5M-A). As a nonlimiting example, Precursor C was bath sonicated at 35 kHz in a sealed borosilicate glass vessel for 1 hour at 38 °C to yield a stable mini-emulsion having a viscosity of ~ 4 cP (cP = 10’3 Pa-s) with sub-500-nm colloids. As another nonlimiting example, a larger volume of Precursor C was homogenized in a high-shear batch emulsifier using a high- shear perforated square-hole stator with a 2.5-inch diameter workhead operating at between 5,000 - 10,000 RPM and at temperature between 25 - 60 °C for 90 minutes in a cylindrical HDPE vessel to yield a stable micro-emulsion with colloids of a mean diameter of 2000 nm. Mini- emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
[00123] The aforementioned final water-based solution was then used to treat two separate fibrous materials; namely, 100% cotton fabric and a cotton/polyester blend fabric. The fibrous substrate materials were treated with the solution by immersing the samples in a solution bath. After fully wetting the samples, excess solution was removed by suspending the saturated sample in the air until enough solution was drained from the sample to attain a target %-weight pick-up ranging between 125 - 150 % (wt./wt.). The samples were then allowed to air dry/cure for 30 minutes under a hot-air blower at 40 °C, cured in a forced-draft oven at 80 °C for 30 min, then acclimated to room conditions for 30 minutes prior to efficacy evaluation.
[00124] The following test methods were conducted to evaluate the surface energy of the treated samples at the air-fiber materials interface: AATCC Test Method 193-2012. Correspondingly, treated samples received a mean ALR grade of 4 on 100% cotton fabric and a mean ALR grade of 4 on a cotton/polyester blend fabric. All treated fabric samples remained soft to the touch with excellent post-treatment hand of fabric. Treated 100% cotton fabric samples subjected to leaching studies using a dynamic leaching procedure adapted from ASTM E2149-13a exhibited no appreciable/detectable levels of analyte in leachate (corresponding to < 10 ppm) after 1 hour of simulated leaching in deionized water and subsequent 1 hour of simulated leaching in nonionic surfactant using a potentiometric titration technique implementing sodium lauryl sulfate as a titrant adapted from ASTM D5806-95 (2017). Comparably, fabrics samples treated with 1 w/v % BENZETHONIUM CHLORIDE (with no covalent interactions with the fabrics) exhibited 50.1 % of analyte in leachate (corresponding to 88.9 ppm) after one hour of simulated leaching in deionized water and an additional 6.6 % (corresponding to 11.5 ppm) of analyte in leachate after another hour of simulated leaching in nonionic sulfactant solution.
[00125] The following describes a synthesis procedure for waterborne, biocompatible, non- cytotoxic, breathable, virucidal/bactericidal, non-leaching coating compositions that also renders the coated surface permanently hydrophobic and a one-stage wet-chemical treatment process for treating porous fiber materials with said coating compositions:
Example II
[00126] A precursor solution of methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane (CAS: 102782-92-3/75718-16-0) (i.e., poly(3-((2- aminoethyl)amino)propyl)methyl(dimethyl)siloxane) in a co-solvent blend of methyl acetate, 4- chlorobenzotrifluoride, and dimethyl carbonate was prepared under stirring (Precursor A). A designated amount of Precursor A was heated to a temperature of 40 °C under stirring. After 5 minutes, specific amounts of bonding agent (3-glycidoxypropyl)trimethoxysilane was added to initiate nucleophilic addition with primary amine groups of the graft polymer backbone agent via an SN2-type epoxide ring-opening mechanism. After 5 minutes, hydrophobing and plasticizer agent n-propyltrimethoxysilane was added followed by designated amounts of nonionic emulsifying agent di(propylene glycol)monomethyl ether. After 2 minutes, specific amounts of active compound N,N-didecyl-N-methyl-N-(3 -trimethoxy silylpropyl)ammonium chloride and co-solvent methanol were slowly added concomitantly followed by a designated amount of nonionic emulsifying agent isodecyl alcohol ethoxylate (CAS: 78330-20-8). A single-phase, homogeneous, transparent solution was obtained (Precursor B2). After 2 minutes, all added deionized water was slowly added to Precursor B2 at a rate of ~ 50 mL/s under vigorous stirring. A white, turbid, macroscale, homogeneous colloidal suspension was immediately obtained with a pH between 5.5 and 7, and no indication of flocculation or aggregation was observed.
[00127] The resulting colloidal suspension (Precursor C2) was mechanically emulsified using ultrasonication techniques. As a nonlimiting example, Precursor C2 was bath sonicated at 35 kHz in a sealed borosilicate glass vessel for 1 hour at 38 °C to yield a stable mini-emulsion with sub- 500-nm colloids. Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
[00128] The aforementioned final water-based solution was then used to treat two separate fibrous materials; namely, 100% cotton fabric and a cotton/polyester blend fabric. The fibrous substrate materials were treated with the solution by immersing the samples in a solution bath. After fully wetting the samples, excess solution was removed by suspending the saturated sample in the air until enough solution was drained from the sample to attain a target %-weight pick-up ranging between 125 - 150 % (wt./wt.). The samples were then allowed to air dry/cure for 30 minutes under a hot-air blower at 40 °C, cured in a forced-draft oven at 80 °C for 30 min, then acclimated to room conditions for 30 minutes prior to efficacy evaluation.
[00129] The following test methods were conducted to evaluate the surface energy of the treated samples at the air-fiber materials interface: AATCC Test Method 193-2012. Correspondingly, treated samples received a mean ALR grade of 4 on 100% cotton fabric and a mean ALR grade of 4 on a cotton/polyester blend fabric. All treated fabric samples remained soft to the touch with excellent post-treatment hand of fabric. Treated 100% cotton fabric samples subjected to leaching studies using a dynamic leaching procedure adapted from ASTM E2149-13a exhibited no appreciable/detectable levels of analyte in leachate (corresponding to < 10 ppm) after 1 hour of simulated leaching in deionized water and subsequent 1 hour of simulated leaching in nonionic surfactant using a potentiometric titration technique implementing sodium lauryl sulfate as a titrant adapted from ASTM D5806-95 (2017). Comparably, fabrics samples treated with 1 w/v % BENZETHONIUM CHLORIDE (with no covalent interactions with the fabrics) exhibited 50.1 % of analyte in leachate (corresponding to 88.9 ppm) after one hour of simulated leaching in deionized water and an additional 6.6 % (corresponding to 11.5 ppm) of analyte in leachate after another hour of simulated leaching in nonionic sulfactant solution.
[00130] The following describes a synthesis procedure for waterborne, biocompatible, non- cytotoxic, breathable, virucidal/bactericidal, non-leaching coating compositions that also renders the coated surface permanently hydrophobic and a one-stage wet-chemical treatment process for treating porous fiber materials with said coating compositions:
Example III
[00131] A precursor solution of methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane copolymer (CAS: 102782-92-3/75718-16-0) (i.e., poly(3- ((2-aminoethyl)amino)propyl)methyl(dimethyl)siloxane) in a co-solvent blend of methyl acetate, 4-chlorobenzotrifluoride, and dimethyl carbonate was prepared under stirring (Precursor A). A designated amount of Precursor A was heated to a temperature of 40 °C under stirring. After 5 minutes, specific amounts of bonding agent (3-glycidoxypropyl)trimethoxysilane was added to initiate nucleophilic addition with primary amine groups of the graft polymer backbone agent via an SN2-type epoxide ring-opening mechanism. After 5 minutes, hydrophobing and plasticizer agent n-propyltrimethoxysilane was added followed by designated amounts of nonionic emulsifying agent di(propylene glycol)monomethyl ether. After 2 minutes, a designated amount of nonionic emulsifying agent isodecyl alcohol ethoxylate (CAS: 78330-20-8) was added followed by specific amounts of active compound octadecyldimethyl(3-trihydroxysilylpropyl)ammonium chloride (CAS: 199111-50-7) (i.e., polysilsesquioxane steardimonium chloride) in oligomeric/polymeric powdered form, where bath ultrasonication at 35kHz for 2 minutes was used to wet and disperse the polysilsesquioxane steardimonium chloride powder. A single-phase, homogeneous, translucent solution was obtained (Precursor B3). After 2 minutes, all added deionized water was slowly added to Precursor B3 at a rate of ~ 20 mL/s under vigorous stirring. A white, turbid, macroscale, homogeneous colloidal suspension was immediately obtained with a pH between 5.5 and 7 - no indication of flocculation or aggregation was observed.
[00132] The resulting colloidal suspension (Precursor C3) was mechanically emulsified using ultrasonication techniques. As a nonlimiting example, Precursor C3 was bath sonicated at 35 kHz in a sealed borosilicate glass vessel for 1 hour at 38 °C to yield a stable mini-emulsion with sub- 500-nm colloids. Mini-emulsions/nano-emulsions with a mean colloid diameter between 200 - 2000 nm with a narrow dispersity are preferred for the waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching, hydrophobic coating compositions discussed herein.
[00133] The aforementioned final water-based solution was then used to treat two separate fibrous materials; namely, 100% cotton fabric and a cotton/polyester blend fabric. The fibrous substrate materials were treated with the solution by immersing the samples in a solution bath. After fully wetting the samples, excess solution was removed by suspending the saturated sample in the air until enough solution was drained from the sample to attain a target %-weight pick-up ranging between 125 - 150 % (wt./wt.). The samples were then allowed to air dry/cure for 30 minutes under a hot-air blower at 40 °C, cured in a forced-draft oven at 80 °C for 30 min, then acclimated to room conditions for 30 minutes prior to efficacy evaluation.
[00134] The following test methods were conducted to evaluate the surface energy of the treated samples at the air-fiber materials interface: AATCC Test Method 193-2012. Correspondingly, treated samples received a mean ALR grade of 4 on 100% cotton fabric and a mean ALR grade of 4 on a cotton/polyester blend fabric. All treated fabric samples remained soft to the touch with excellent post-treatment hand of fabric. Treated 100% cotton fabric samples subjected to leaching studies using a dynamic leaching procedure adapted from ASTM E2149-13a exhibited no appreciable/detectable levels of analyte in leachate (corresponding to < 10 ppm) after 1 hour of simulated leaching in deionized water and subsequent 1 hour of simulated leaching in nonionic surfactant using a potentiometric titration technique implementing sodium lauryl sulfate as a titrant adapted from ASTM D5806-95 (2017). Comparably, fabric samples treated with 1 w/v % BENZETHONIUM CHLORIDE (with no covalent interactions with the fabrics) exhibited 50.1 % of analyte in leachate (corresponding to 88.9 ppm) after one hour of simulated leaching in deionized water and additional 6.6 % (corresponding to 11.5 ppm) of analyte in leachate after another hour of simulated leaching in nonionic sulfactant solution.
[00135] The following describes a method for filtering viral particles to reduce viral transmission using air filtration media treated with a waterborne, biocompatible, non-cytotoxic, breathable, virucidal/bactericidal, non-leaching coating composition: Example IV
[00136] Filtering SARS-CoV-2: Initial investigation of viral transmission was done on a MVTR-A1 -treated tri-pleat air filter having a Minimum Efficiency Reporting Value (MERV) of 8 (“treated MERV 8”), an untreated tri-pleat air filter having a MERV of 8 (“untreated MERV 8”), and an untreated tri-pleat air filter having a MERV of 13 (“untreated MERV 13”). MERVs report a filter’s ability to capture larger particles between 0.3 and 10 microns (pm). This value is helpful in comparing the performance of different filters. The rating is derived from a test method developed by the American Society of Heating, Refrigerating, and Air Conditioning Engineers (ASHRAE). The higher the MERV rating the better the filter is at trapping specific types of particles.
[00137] Transmission of SARS-CoV-2 virions through common HVAC air-filtration media was simulated by fixing the treated and untreated MERV 8 and the untreated MERV 13 air filters with a metal mesh support flush in-contact behind a target area of the experimental filter, as illustrated in FIG. 3. A partial air draft through the filter was imparted using a box-fan. With the combined experimental filter and collection and retention filter arrangement fixed to front face of the box-fan with an incident air velocity of 0.67m/s, 1.0 mL of a thermally-inactivated SARS- CoV-2 inoculum was sprayed onto a target area (~7 cm x ~7 cm) on the front face of the experimental air-filter from a distance of 5 cm orthogonal to the face of the filter. Embodiments of the disclosure having a coated substrate may refer to a filter for HVAC applications with an applied coating according to one or more embodiments of this disclosure similar to the experimental filter configuration of FIG. 3.
[00138] The retention filter was then carefully removed, eluted, and concentrated prior to running RT-qPCR amplification cycles. Collection and retention filter swatches were eluted in a phosphate buffered saline (pH = 7.4) with 0.05% (v./v.) TWEEN® 20 (aq.) for 1 hour. The eluent was centrifugally concentrated 6.7 times volumetrically using tangential flow filtration with a 100,000 molecular weight cut-off (MWCO) membrane. Virions were then lysed by adding TRITON™ X-100 to a concentration of 30 vol.%. Concentrated samples were tested with the N1 primer set for COVID-19 using the LUNA® Universal One-Step RT-qPCR Kit (New England Biolabs, Inc.) using a Chai Open qPCR instrument (Chai, Inc.). Relative fluorescence yield was measured, which was also dependent on the number of qPCR cycles. The untreated MERV 8 and untreated MERV 13 filters behaved as expected, with the untreated MERV 13 outperforming the untreated MERV 8 (FIG. 4). The treated MERV 8 demonstrated the best performance, with no detectable amounts of virus passing through the treated filter (FIG. 4).
[00139] These results were corroborated by a follow-up independent study using a slightly modified experimental procedure. An untreated tri-pleat air filter having a MERV of 11 (“untreated MERV 11”) and an untreated tri-pleat air filter having a MERV of 14 (“untreated MERV 14”) were also tested in addition to the untreated MERV 8 and 13 filters and treated MERV 8 filter. With air drawn through the filter at a mean incident air velocity of 0.67 m/s and AN air temperature of 24.7 °C, a target area (7.5 cm x 7.5 cm) on the front face of the experimental filter was sprayed with 1.0 mL of inoculum at a viral titer of 1.0 million genomes/mL. The collection and retention filter was carefully removed and eluted. Collection and retention filter swatches (FPR-10) were eluted in 100 mL of 1% beef extract/0.05M glycine (pH 9) for 20 min. The eluent was concentrated to a final volume of 1.6 mL using a combination of tangential flow filtration and centrifugal ultrafiltration. Subsequently, 50 pL of each sample was treated with 6.5 pL of
Proteinase K, then incubated at 60 °C (15 min)/98 °C (5 min) prior to running RT-qPCR. [00140] RT-qPCR was conducted using 7 pL samples in triplicate using a Chai Open qPCR instrument (Chai, Inc.). Gloves were changed between samples to minimize cross-contamination. A larger cycle quantification value (Cq) indicates a smaller initial concentration of captured thermally-inactivated SARS-CoV-2 virions extracted from the collection filter, which corresponds to an increase in virion-filtration performance. The data demonstrate that as the MERV rating increases, the cycle quantification requires a larger number of amplification/denaturation cycles before onset of fluorescence, as less viral load penetrates the experimental filters. The treated filters are far more effective than even the MERV 14 and substantially reduce transmission to a negligible rate, as shown in FIG. 5.
[00141] Cycle quantification values were also compared to filter efficiency, as shown in FIG. 6. The x-axis represents MERV ratings for different filters, the left y-axis is the cycle quantification value, and the right y-axis represents the theoretical efficiency of the filters when dealing with virions smaller than 0.3 pm. Two lines are shown, with the first line (•) depicting the actual cycle quantification values determined and the second line ( — ) representing a theoretical estimation of the cycle quantification values that the filters should yield depending on the efficiency of the filter. This data shows that the performance of MVTR-A1 -treated MERV 8 filter performs equivalent to or better than what would be expected for a MERV 14 or 16 filter.
[00142] In order to determine if the filters immobilize the virus on the front face, swab tests were also performed on the front face of the filter. Samples were taken from the same 3 pleats in the immediate target area at increasing exposure time to a constant draft of air at an incident air velocity of 0.71 m/s and air temperature of 23.0 °C, orthogonal to the filter face plane. Initially, we found significant number of virions on the front face as seen in FIG. 7. However, after 30 minutes no detectable amounts of RNA could be found because the virions decompose to constituent nucleotides upon desiccation. The same procedure was conducted on the back face of the filter to corroborate these results, where no evidence of virion transmission was detectable.
[00143] Filter Efficiency. Regarding fiber efficiency for filters, the total efficiency (ET) is dependent on the efficiency of the inertial impaction (En), the diffusion (ED), the interception (Eit), a combination of the interception and diffusion (EDU), and finally gravity (EG): ET = (Eii+Eo+Eit+EDit+Eo). Additionally, in fluid dynamics, the passage of certain materials (shape and size of the particles within the fluids) through the filter system is dependent on the viscosity and flow, which has a knock-on effect on the laminar flow governed by Stokes law or the Peclet number, which is how the thermal energy of the molecules cause a net velocity perturbation on the particle.
[00144] For a sphere like SARS-CoV-2, the flow rate is determined by diameter of the particle size, viscosity of the fluid, and speed of the fluid through the air. As the particles traveling in an aqueous medium through the air drift through the filters, they are governed by factors including drag force, comprising fluid or friction resistance, and are thus impacted by the in-path filter. The pressure drops along the contact length between the fiber boundaries and flow of the fluid and particle (also known as the Bejan number), as does the momentum and mass diffusivity (also known as the Schmidt number). If the particles or the droplets are larger than 10 pm, they will most likely impact on the surface of the filter fibers. However, there is a risk that on impact, the larger particle-containing fluid could break up, and with the positive airflow through the filters, the smaller particle-containing fluid droplets could be pulled through. The smaller particles are then more governed by the Peclet number; and diffusion of the particles is inversely proportional to the Peclet number. The filter efficiency continues to decrease, as shown in FIG. 8, until particle size decreases below the penetrating particle size for most filter systems — less than 120 nm. The graph of FIG. 8 shows several lines corresponding to filter efficiency. The bottom line corresponds to MERV 6, which each higher line sequencing through MERV 8, 11, 12, 13, 14, 15, and 16 for the top-most line.
[00145] In the case of SARS-CoV-2, the challenge is that the virus is too large for the Peclet number to affect its passage and, in some embodiments, the virus may be filtered like solid state particles normally handled by MERV 13-16 filters. The particle diffusion length DSE is defined by DSE = kTCc/37rr|dpd, where k is Boltzman’s constant, T is temperature, Cc is the Cunningham slip factor, T] is the dynamic viscosity of the carrier gas in kg/m-s, and dp is the particulate diameter. The Cunningham slip factor is Cc = 1 + Kn(Ai+A2Exp (-Asd/X)), where Kn relates the gas molecular mean free path (r|) to the particle size (dp), and in the present experiment in air, Ai = 1.142, A2 = 0.558 and A3 = 1.998. This means Cc = l+Kn(1.142+0.558Exp(-0.999d/X)). When Kn » 1, particles follow along the slip regime, while for Kn « 1, particles follow along molecular free flow. For the solid particulate of the coronavirus, which has a diameter (d) of ~ 120 nm and a mean free path in air at normal pressure of 65 nm, the Kn value is ~ 1.1, which results in particles that are much more likely to follow molecular free flow of air, implying closeness to diffusion transitions instead of particles affected by interception filtration.
[00146] Table 1 uses data from the FIG. 9 to determine where the filter efficiency overlaps with the particle size of SARS-CoV-2. Even with the highest-rated filter, there is still a risk the virus will pass through — it would take 3 or 4 passes of the same air through the same filters to clean the air almost completely and remove the risk of passing on the virus.
Table 1
Figure imgf000074_0001
Figure imgf000075_0001
[00147] Material Coating on Filters and Analysis'. In order to elucidate the chemical structure information of the MVTR-A1 -coated cotton fibers, a state-of-the-art optical-photothermal infrared (O-PTIR) microspectroscopy technique with simultaneous Raman microspectroscopy (O- PTIR+R) was used, where selective absorbance of mid-IR excitation laser light is detected using a visible light probe laser (532 nm) via a photothermally-induced thermal lensing effect.
[00148] The O-PTIR+R technique was non-contact and utilized tunable pulsed mid-IR laser light (5.5 - 12 pm) from a QCL to excite a selected spot on a sample under ambient conditions, producing transmission-mode FTIR-quality spectra at submicron spatial resolution. Using the O- PTIR+R technique, IR absorbance is measured through energy and position changes in scattered 532-nm laser light due to localized shifts in refractive index from the sample at laser foci. By using such a detection mechanism, O-PTIR+R bypasses the wavelength-dependent diffraction limit of IR light (5 - 12 pm) and resolves interfacial regions with submicron resolution and remarkable chemical specificity. Averaged O-PTIR spectra of pristine/untreated and treated cotton are provided in FIG. 9A. Averaged Raman spectra of pristine/untreated and treated cotton are provided in FIG. 9B.
[00149] Although the present disclosure and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the design as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the present disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present disclosure. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

What is claimed is: A biocidal composition, comprising: water; at least one co- solvent; at least one biocidal compound; at least one graft polymer backbone agent; and at least one emulsifying agent. The biocidal composition of claim 1, wherein at least one of: the at least one co-solvent comprises methyl acetate, 4-chlorobenzotrifluoride, dimethyl carbonate, and methanol, the at least one active biocidal compound comprises octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, the at least one graft polymer backbone agent comprising methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane, and the at least one emulsifying agent comprises isodecyl alcohol ethoxylate; the at least one co-solvent comprises methyl acetate, 4-chlorobenzotrifluoride, dimethyl carbonate, and methanol, the at least one active biocidal compound comprises N,N- didecyl-N-methyl-N-(3 -trimethoxy silylpropyl)ammonium chloride, the at least one graft polymer backbone agent comprising methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane, and the at least one emulsifying agent comprises di(propylene glycol)monomethyl ether; or the at least one co-solvent comprises methyl acetate, 4-chlorobenzotrifluoride, and dimethyl carbonate, the at least one active biocidal compound comprising octadecyldimethyl(3 -trihydroxy silylpropyl)ammonium chloride, the at least one graft polymer backbone agent comprises methoxy-Zhydroxy-terminated aminoethylaminopropylmethylsiloxane, and the at least one emulsifying agent comprising di(propylene glycol)monomethyl ether and isodecyl alcohol ethoxylate.
75
3. The biocidal composition of claim 1, wherein the at least one co-solvent comprises methanol, ethanol, phenoxyethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol acetone, acetonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, di(propylene glycol) methyl ether, 4-chlorobenzotrifluoride, odorless mineral spirits/petroleum distillates, or a mixture thereof.
4. The composition of claim 1, wherein the at least one active biocidal compound comprises at least one of a quaternary ammonium, a phosphonium compound, a tertiary sulfonium compound, a polymeric compound, a polyionic compound, a metal salt, a metal nanoparticle, a metal-oxide nanoparticle, a reactive oxygen-generating species, a N-halamine, a biomacromolecule, or derivatives thereof.
5. The composition of claim 4, wherein the at least one active biocidal compound comprises at least one of: a silyl ether quaternary ammonium and/or phosphonium compound, an alkoxysilyl quaternary ammonium, a phosphonium compound, a hydroxysilyl quaternary ammonium, a phosphonium compound, a silyl halide quaternary ammonium, a phosphonium compound, a silyl ether tertiary sulfonium compound, an alkoxysilyl tertiary sulfonium compound, a hydroxysilyl tertiary sulfonium compound, a silyl halide tertiary sulfonium compound, a polyacrylic acid, polymethacrylic acid, polyethylacrylic acid, polypropylacrylic acid, polyvinylbenzoic acid, or a copolymer of any combination of acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid and vinylbenzoic acid.
6. The composition of claim 1, wherein the at least one graft polymer backbone agent comprises at least one of: an alkoxyalkylsilane; a silicone and/or siloxane oligomer, co-oligomer, polymer, or co-polymer, or a combination thereof; or a silicone and/or siloxane oligomer, co-oligomer, polymer, or co-polymer, or a combination thereof, in combination with a substituted/unsubstituted alkyl functional silyl ether, halogensilane, or silyl hydride.
76
7. The composition of claim 1, wherein the at least one emulsifying agent comprises at least one of: a nonionic amphiphilic monomer, oligomer, co-oligomer, polymer, or co-polymer, or a combination thereof; or an ethoxylated nonionic amphiphilic monomer, oligomer, co-oligomer, polymer, or copolymer, or a combination thereof.
8. The composition of claim 1, further comprising one or more functional additives comprising at least one of a base compound, a bonding agent, a plasticizer, a hydrophobing agent, or a chelating agent.
9. The composition of claim 8, wherein: the base compound comprises a compound having the formula M(OR6)4, wherein:
M is Si, Al, Ti, In, Sn, or Zr, and
R6 is a hydrogen, a substituted or unsubstituted alkyl group, or a derivative thereof; the bonding agent comprises a compound having the formula M(OR7) R8 y R9 Z, wherein:
M is Si, Al, In, Sn, or Ti,
R7 is a hydrogen, a substituted or unsubstituted alkyl group, or a derivative thereof, R8 is a hydrogen, a substituted or unsubstituted alkyl group or a derivative thereof, R9 is a substituted or unsubstituted epoxy or glycidoxy group, x and z are each independent integers from 1 to 3, y is an integer from 0 to 2, and the sum of x, y and z is 4; the plasticizer comprises a compound having the formula M(OR10)4-I R11^, wherein:
M is Si, Al, In, Sn, or Ti,
R10 is a hydrogen, a substituted or unsubstituted alkyl group, or a derivative thereof,
R11 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or a derivative thereof, and x is 1, 2 or 3; and
77 the chelating agent comprises an alkoxysilane and/or a metal oxide precursor having the formula M(0R12)^ R13? R14 z, wherein: M is Si, Al, In, Sn, or Ti,
R12 includes a hydrogen, a substituted or unsubstituted alkyl group, or a derivative thereof,
R13 includes a hydrogen, a substituted or unsubstituted alkyl group, or a derivative thereof,
R14 includes a substituted or unsubstituted alky or alkenyl group having from 3 to 20 carbon atoms, a substituted or unsubstituted amine, or a thiol, x and z are each independently an integer from 1 to 3, y is an integer from 0 to 2, and the sum of x, y, and z is 4. The biocidal composition of claim 1, wherein the biocidal composition comprises an emulsion with a mean colloid diameter between 200 nm and 2000 nm. A method of preparing a biocidal composition comprising water, at least one co-solvent, at least one biocidal compound, at least one graft polymer backbone agent, and at least one emulsifying agent, the method comprising: mixing the at least one co-solvent and at least one graft polymer backbone agent to form a first mixture; adding the at least one active biocidal compound and the at least one emulsifying agent to the first mixture to form a second mixture; adding the water to the second mixture to form a third mixture comprising a colloidal suspension; and emulsifying the third mixture. The method of claim 11, further comprising: adding to the second mixture at least one of a base compound, a bonding agent, a hydrophobing agent, a plasticizer, or a chelating agent.
78 The method of claim 11, wherein emulsifying the third mixture comprises mechanically emulsificating using ultrasonication, a high-pressure homogenizer, or a high-shear emulsifier. A method of preparing a biocidal substrate, comprising: coating a substrate with a biocidal composition comprising water, at least one co-solvent, at least one biocidal compound, at least one graft polymer backbone agent, and at least one emulsifying agent; and treating the coated substrate to remove the water and co-solvents and to cure the coated substrate. The method of claim 14, wherein the substrate comprises at least one of fabrics, textiles, fibers, garments, personal protective equipment, masks, respirator masks, filters, plastics, tarpaulin-type material, cellulose semi-permeable membranes, masonry, concrete, stone, brick, stucco, grout, wood-based products, fences, decks, furniture, or porous ornaments. The method of claim 14, wherein coating the substrate comprises spraying, misting, doctor-blading, padding, foaming, flooding, dipping, rolling, or inkjet printing the biocidal composition onto the substrate, and wherein the biocidal composition soaks, penetrates, permeates, is layered on, and/or is bonded to the substrate. The method of claim 14, wherein treating the coated substrate causes at least one active biocidal compound to at least one of: form covalent bonds with the at least one graft polymer backbone agent; or be physically entrapped or encapsulated in a covalent network provided by the at least one graft polymer backbone agent. The method of claim 17, wherein treating the coated substrate comprises at least one of imparting the substrate with the at least one active biocidal compound or preventing leaching of the at least one active biocidal compound from the substrate The method of claim 18, wherein leaching of the at least one active compound is at least 95% inhibited.
79 The method of claim 14, wherein the treating the coated substrate produces a biocidal- coated substrate protecting against at least one of an infectious agent, a contagion, or a pathogen that causes infectious diseases by deactivating, inhibiting, terminating, or lysing the at least one of an infectious agent, a contagion, or a pathogen.
80
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