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EP2348837A2 - Enduction pour le contrôle des maladies - Google Patents

Enduction pour le contrôle des maladies

Info

Publication number
EP2348837A2
EP2348837A2 EP09777997A EP09777997A EP2348837A2 EP 2348837 A2 EP2348837 A2 EP 2348837A2 EP 09777997 A EP09777997 A EP 09777997A EP 09777997 A EP09777997 A EP 09777997A EP 2348837 A2 EP2348837 A2 EP 2348837A2
Authority
EP
European Patent Office
Prior art keywords
compound
alkyl
group
heteroalkyl
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09777997A
Other languages
German (de)
English (en)
Inventor
Jeffrey Owens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alexium Ltd
Original Assignee
Alexium Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/362,890 external-priority patent/US8815351B2/en
Application filed by Alexium Ltd filed Critical Alexium Ltd
Publication of EP2348837A2 publication Critical patent/EP2348837A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to coatings for disease control.
  • Toxins are biologically-derived molecules that cause disease. They include prions, proteins, polysaccharides, enzymes, nucleic acids and histones. They are, by definition, non-living in contrast to other disease vectors such as pathogens.
  • the present invention aims to address at least some of the problems of the prior art. Accordingly, the present invention provides in a first aspect a method for forming a coating on a substrate for deactivation of toxins, the method comprising: providing a compound containing a glycoluril functional group and a siloxane monolayer precursor group, applying the compound to the surface, and exposing the surface to microwave electromagnetic radiation.
  • the present invention provides a method for forming a coating for deactivation of toxins on a substrate, the method comprising: providing a compound containing a functional group containing at least two hydrogen atoms attached to one or more nitrogen atoms and a compound containing a cross-linking siloxane precursor group and applying the compounds to the surface.
  • the present invention provides substrate having a coating attached to, and / or organised into an array on a surface by being treated by the method of the first or second aspects.
  • the present invention provides a compound having the structure:
  • R 1 , R 2 , R3 and R 4 , R 5 and R 6 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl, a group containing a siloxane monolayer precursor, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl), and at least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a group containing a siloxane monolayer precursor.
  • the present invention provides a compound having the structure: wherein: X 1 and X 2 are independently-selected heteroatoms, optionally having one or more pendant independently-selected alkyl and / or independently-selected heteroalkyl groups and / or hydrogen, R 1 , R 2 , R 3 and R 4 , R 5 and R 6 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl), and at least one of R 1 , R 2 , R3, R 4 , R5 and R 6 is a group containing a vinyl group, an imide, an acrylate, an alkene, an epoxide or
  • the present invention provides a method for forming a coating for deactivation of toxins on a substrate, the method comprising: providing the compound of the fifth aspect, applying the compound to the surface, and exposing the surface to microwave electromagnetic radiation.
  • the present invention provides a substrate having a compound containing a glycoluril functional group attached to, and / or organised into an array on the surface by the method as defined in the sixth aspect.
  • the present invention also provides the use of a coating formed from a compound containing a glycoluril functional group and a siloxane monolayer precursor group in the deactivation of toxins.
  • the present invention also provides the use of a coating formed from by the method as defined in the first aspect in the deactivation of toxins.
  • the present invention provides a method for forming a coating on a substrate, the method comprising: providing a compound containing a glycoluril functional group and a compound containing a cross-linking siloxane precursor, and applying the compound to the surface.
  • the inventor of the present invention has found a class of molecules that is effective against toxins when attached to a surface in a particular way.
  • This molecule includes a glycoluril functional group.
  • the molecule further includes a siloxane monolayer precursor group so that the glycoluril functional group is attached to a surface and / or organised into an array at the surface by reaction of the surface with the siloxane monolayer precursor.
  • this molecule would be attached to the surface by heat treatment as in US 6969769.
  • this method of attachment of the molecule to the surface does not result in a surface that is effective against toxins. Instead, the inventor has found that it is necessary to attach this molecule and other molecules containing a N-halogen bond to a surface under the irradiation of microwaves in order for them to form a surface that is effective against toxins.
  • the present invention provides a method for attaching compounds containing both a glycoluril functional group and a siloxane monolayer precursor group to a surface by exposing the surface to the compound while being treated with microwaves.
  • the first aspect also more broadly provides a process for deactivating toxins, the process comprising: exposing a toxin to a coating deposited on a substrate, wherein the coating comprises an N-halogen group.
  • the N-halogen group is contained in a compound containing a functional group selected from the group consisting of hydantoin, imidazolidinone, glycoluril, iscyanurate and triazinedione.
  • the halogen appends one of the nitrogen atoms contained in a of hydantoin, imidazolidinone, glycoluril, iscyanurate or triazinedione group.
  • the inventor has found a way in which a surface may be provided having a density of N-halogen bonds to be effective against toxins, namely by deposition of the compounds containing the N-halogen group(s) or precursors to the N-halogen groups(s) under the treatment of microwaves.
  • the coating is deposited by the method of the second aspect of the invention in combination with microwave irradiation.
  • microwaves preferably refers to electromagnetic radiation having a frequency from 0.3 to 30 GHz.
  • the microwaves have a frequency of 0.3 to 10 GHz, more preferably from 1 to 3 GHz.
  • the microwaves are actively applied to the substrate by, for example, a microwave power source.
  • the microwaves may be produced using a power rating of 650 Watts or less, for example 65 to 650 Watts, such as 135 to 400 Watts.
  • siloxane monolayer precursor refers to a group that is able to form a siloxane monolayer at the surface of a substrate. Siloxane monolayer precursors are well-known to the person skilled in the art.
  • the surfaces for use in the present invention contain a number of nucleophilic sites on their surface, so reaction of the siloxane monolayer precursor with a surface typically involves the nucleophilic displacement of a leaving group attached to the silicon by one of the nucleophilic sites on the surface of the substrate.
  • the siloxane monolayer precursor may also react with other siloxane monolayer precursor molecules in a cross-linking reaction to from the Si-O-Si (siloxane) functional group to form an organised array of molecules.
  • siloxane monolayer precursor includes within its scope pre-formed siloxane groups, such as siloxane polymers. This overall process is known as the self-assembly of a monolayer at the surface.
  • siloxane monolayer precursor does not require the formation of a complete monolayer over the surface of a substrate. In fact, the formation of a complete surface-covering monolayer involves the careful control of reaction conditions and selection of precursors. Rather, the term simply requires that some of the siloxane monolayer precursor groups contain groups such as leaving groups that can be displaced by nucleophiles that can react with the surface of a substrate.
  • the precursor may also be able to self-react with other siloxane monolayer precursor molecules (self-reaction usually occurs after the displacement of a leaving group with, for example, water, followed by reaction of the newly formed Si-OH with a second siloxane monolayer precursor).
  • self-reaction usually occurs after the displacement of a leaving group with, for example, water, followed by reaction of the newly formed Si-OH with a second siloxane monolayer precursor.
  • the term does not exclude precursor molecules that form multilayers rather than single monolayers.
  • Siloxane monolayer precursors include compounds containing silicon-X 3 functional groups, wherein X 3 is a leaving group.
  • X 3 may be, for example, a halogen, O-alkyl, O-heteroalkyl, OH, NH 2 , NH-alkyl, NH-heteroalkyl, N(alkyl)(alkyl), N(alkyl)(heteroalkyl) or N(heteroalkyl)(heteroalkyl).
  • Siloxane monolayer precursors also include pre-formed siloxane polymers themselves.
  • the siloxane monolayer precursor may be selected from a siloxane compound, a silanol compound, a silyl ether compound, a silanolate compound, a halosilane compound, a silatrane compound and a silazane compound.
  • glycol functional group refers to a compound containing the following chemical structure:
  • Xi and X 2 are independently-selected optionally-substituted heteroatoms (i.e. atoms other than carbon).
  • the heteroatoms may be substituted with one or more independently-selected alkyl and / or heteroalkyl groups (as defined below) and / or hydrogen as appropriate.
  • X 1 and / or X 2 may be oxygen, nitrogen or sulphur. If either or both of X 1 or X 2 is nitrogen or another atom having a valency of three or more, X 1 and / or X 2 is substituted with further substituents.
  • X 1 and / or X 2 may have the chemical formula NR 7 .
  • R 7 (or any other substituent(s)) is hydrogen.
  • R 7 (or any other substituent(s) on any heteroatom) may be OH, O-alkyl, O-heteroalkyl, alkyl or heteroalkyl. It is to be noted that the carbon-carbon bond shown in the above structure may be a single bond or a double bond.
  • alkyl refers to a group containing carbon and hydrogen.
  • An alkyl group contain any number of carbon atoms. Preferably, the alkyl group contains 1 to 25 carbon atoms. More preferably, the alkyl group contains 1 to 10 carbon atoms, for example 1 to 6 carbon atoms.
  • the alkyl group may itself be unsubstituted (i.e. contain only carbon and hydrogen) or, alternatively, it may be substituted with heteroatom-containing substituents.
  • the alkyl group may straight-chained or it may be branched or it may cyclic, or combinations thereof.
  • the alkyl group may be saturated, partially or completely unsaturated or aromatic.
  • the alkyl group may comprise one or more alkene and / or alkyne functional groups.
  • the alkyl group may be or may comprise an aryl group.
  • aryl refers to a group comprising one or more aromatic cycles. The cycle is made from carbon atoms.
  • saturated unsubstituted alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, sec-propyl, cyclopropyl, n-butyl, sec-butyl, fe/ ⁇ -butyl, cyclobutyl, pentyl (branched or unbranched) and hexyl (branched or unbranched).
  • saturated unsubstituted alkyl groups having 1 to 6 carbon atoms further include cyclic carbon compounds, for example a cyclopropyl group, a cylcobutyl group, a cyclopentyl group and a cyclohexyl group.
  • the alkyl group may be partially substituted or completely substituted with one or more independently selected heteroatoms or groups of heteroatoms.
  • the alkyl group may comprise an aldehyde, a ketone, a carboxylic acid or an amide.
  • An example of an aryl substituent is a phenyl group.
  • alkyl may be haloalkyl, such as a haloalkyl in which one or more halo groups is located at the distal end of the alkyl chain from the silicon.
  • the haloalkyl is preferably chloroalkyl.
  • heteroalkyl group refers to a first alkyl group substituted with one or more independently-selected heteroatoms or groups of heteroatoms, which itself is substituted with one or more independently-selected groups containing one or more carbon atoms.
  • a heteroalkyl can be represented by the generic formula R 8 - Y - Rg, where R 8 is an alkyl group, Y is one or more heteroatoms and Rg contains one or more carbon atoms and optionally one or more heteroatoms and connects to Y through a carbon atom (e.g. an alkyl group).
  • heteroatoms in heteroalkyl groups include nitrogen, oxygen, phosphorus and sulfur.
  • Y as defined above is oxygen.
  • Y is a nitrogen atom.
  • R 8 and Rg may be joined to one another so as to form a cyclic group containing one or more heteroatoms.
  • a heteroalkyl group contain any number of carbon atoms.
  • a heteroalkyl group contains a total of 1 to 25 carbon atoms.
  • the heteroalkyl group contains a total of 1 to 10 carbon atoms, for example 1 to 6 carbon atoms.
  • the heteroalkyl group may itself be unsubstituted (i.e. contain only carbon, hydrogen and the heteroatom or groups of heteroatom contained in the backbone of the heteroalkyl group) or, alternatively, it may be substituted with heteroatom-containing substituents.
  • the heteroalkyl group may straight-chained or it may be branched or it may cyclic, or combinations thereof.
  • the heteroalkyl group may be saturated, partially or completely unsaturated or aromatic.
  • the heteroalkyl group may be or may comprise cyclic groups containing a heteroatom. As described above for alkyl groups, the heteroalkyl group may be unsubstituted or substituted with one or more hetero-atoms or group of heteroatoms. Alternatively or in addition, the heteroalkyl group may be substituted with one or more heteroatoms or groups of heteroatoms that are themselves substituted with one or more independently selected alkyl groups.
  • the heteroalkyl group may also be or may comprise a heteroaryl group.
  • heteroaryl refers to group comprising one or more aromatic cycles. The cycle is made from carbon atoms and heteroatoms. The one or more heteroatoms are independently-selected from, for example, nitrogen, oxygen, phosphorus and sulphur.
  • the first aspect of the present invention uses a glycoluril compound having the following structure:
  • X 1 and X 2 are independently-selected optionally-substituted heteroatoms (i.e. atoms other than carbon).
  • X 1 and / or X 2 may be oxygen, nitrogen or sulphur. If either X 1 or X 2 is nitrogen, the nitrogen is substituted with a third substituent, i.e. Xi and / or X 2 have the chemical formula NR 7 .
  • this third substituent (R 7 ) is hydrogen.
  • R 7 (or any optional substituent) may for example be OH, O-alkyl, O-heteroalkyl, alkyl or heteroalkyl.
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl and a siloxane monolayer precursor- containing group.
  • the halogens preferably chlorine or bromine
  • alkyl, heteroalkyl and a siloxane monolayer precursor- containing group Preferably, at least one of R 1 , R 2 , R 3 and R 4 is hydrogen, a halogen (preferably chlorine and / or bromine) or a protecting group for hydrogen (protecting groups are well-known in the art: see, for example, the book “Protective Groups in Organic Synthesis" by Greene et a/.).
  • R 5 and R & are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl and a siloxane monolayer precursor-containing group, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl). At least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a siloxane monolayer precursor-containing group.
  • the at least one siloxane monolayer precursor-containing group may have the following chemical structure:
  • O (3) or a polymer have repeating units of formula (4), which may be terminated by hydrogen, hydroxyl, an alkyl or an amine group at one or both ends of the polymer chain:
  • R 12 is hydrogen or an alkyl group or a heteroalkyl group, preferably a Ci to C 6 alkyl, more preferably, a Ci or C 2 alkyl, such as methyl or ethyl, and m is 1 to 4, preferably 3;
  • leaving groups may replace OR 12 in formula (3) above, for example one or more halogens (e.g. Cl). Leaving groups may also replace R 13 or R 14 in formula (4) above.
  • alkyl and heteroalkyl groups for use in the present invention include groups containing glycidoxy groups, amino groups, acrylates and groups containing alkenes.
  • the polymer defined above preferably includes electron donor groups on at least some of its monomers. These electron donor groups may be substituents on R 13 and / or R 14 in formula (4) above or on on R 13 and / or R 14 and / or R 15 in formula (3) above. Electron donor groups include, but are not limited to, hydroxyl, amine, sulfhydryl and carboxyl.
  • Electron donor groups include, but are not limited to, hydroxyl, amine, sulfhydryl and carboxyl.
  • X the number of repeating units in the polymer, may be any appropriate number. X may be 2 to 10000, preferably 2 to 1000.
  • Ri 2 , R 13 , Ru and / or R 15 are substituted with one or more halogens.
  • the halogens are located at the distal end of the group(s) from the silicon.
  • the halogen is chlorine.
  • the siloxane monolayer precursor-containing compound is a compound of formula (3), wherein m is 3, n is 1 and o and p are both 0, R 12 is hydrogen, methyl or ethyl.
  • At least one of R 13 , R 14 and / or R 15 is of the formula (5):
  • y is 1 to 5, preferably 3.
  • R 5 and / or R 6 is / are a UV-stabilizing group.
  • a solution or suspension of the silicon-containing compounds may be contacted with the surface.
  • the solution and / or suspension preferably comprises a polar solvent, more preferably acetone and / or alcohol, preferably both.
  • the alcohol preferably comprises methanol and / or ethanol.
  • the siloxane monolayer precursor-containing compound may be solvent-free, i.e. not in the form of a solution or suspension, for example in the form of a liquid or gas (but preferably not a plasma).
  • the surface of the substrate is preferably a material having nucleophilic sites on its surface.
  • the nucleophilic sites may comprise one or more nucleophilic groups containing one or more of O, S and N.
  • the nucleophilic groups may be oxygen-containing, nitrogen-containing and / or sulfur-containing, for example selected from OH, SH and NH 2 .
  • the substrate may comprise a fabric material. It has been found that the nucleophilic groups bind to the silicon atoms of the siloxane monolayer precursor-containing compounds on contact and with exposure to microwaves. This reaction normally occurs within seconds, as opposed to hours for conventional methods, such as merely heating.
  • one or more of the following may be used: irradiation at a reduced power level, for example microwaves produced at a power rating of 400 Watts or less, preferably 135 Watts or less, or subjecting the substrate and siloxane monolayer precursor-containing compounds to microwave irradiation and relaxation (i.e.
  • the microwaves can be directed at particular portions of the substrate and therefore allow for regioselective attachment and / or arrangement of the silcon-substituted compounds and for reactions that can be initiated that would not be possible using traditional methods.
  • the substrate may comprise a natural material.
  • the material may be a cloth material.
  • the material may comprise one or more materials selected from cotton, wool and leather.
  • the material may be woven or non-woven.
  • the material may comprise fibres of natural and / or synthetic material.
  • the synthetic material may comprise a woven or nonwoven fabric material to include, but limited to, fabrics wherein the material comprises one or more of cotton, polyester, nylon, wool, leather, rayon, polyethylene, polyvinylchloride, polyvinylalcohol, polyvinylamine and polyurea.
  • the substrate may be in the form of particles.
  • the particles may have a diameter of 10 nm to 1 mm, preferably 100 to 1000 nm.
  • the substrate may comprise a metal oxide.
  • the metal oxide may be selected from one or more of aluminium oxide, titanium dioxide, magnesium oxide, calcium oxide, silicon dioxide and zinc oxide.
  • the substrate may comprise a natural mineral.
  • the substrate may comprise one or more materials selected from kaolinite, barasym, silica, montmorillonite, vermiculite, bohemite and quartz.
  • the substrate may be porous.
  • the substrate may comprise a molecular sieve.
  • the substrate may comprise a zeolite.
  • the substrate may comprise a polymer.
  • the polymer may be in the form of a porous matrix.
  • the substrate may comprise a plastic material.
  • the substrate may comprise polyurethane and / or nylon, plyester, nylon, rayon, polyethylene, polyvinylchloride, polyvinylalcohol, polyvinylamine and polyurea.
  • the substrate may comprise a carbohydrate.
  • an alcohol may be present during deposition of the coating.
  • the substrate may comprise an alcohol.
  • the substrate may have an alcohol on its surface.
  • the alcohol may comprise a diol, which may be a vicinal diol, or a triol.
  • the alcohol may be selected from one or more of an alkyl diol, preferably a C 2 to C 25 alkyl diol, an alkyl trio, preferably a C 3 to C 25 alkyl triol and a phenyl diol, preferably a vicinal phenyl diol.
  • Each hydroxyl group in the triol is preferably vicinal to one of the other hydroxyl groups.
  • the alcohol may be selected from catechol, ethylene glycol or glycerol.
  • the substrate may comprise a silicon dioxide based material, such as glass, silicon dioxide, sand and silica.
  • the glycoluril group should have at least one of its nitrogen substituted with a halogen, for example chlorine or bromine (i.e. at least one or R 1 , R 2 , R3 and R 4 should be a halogen).
  • a halogen for example chlorine or bromine
  • the halogen may be introduced at any stage. For example, it may be introduced prior to the deposition of the coating on the substrate. Alternatively, it may be introduced after the deposition of the coating on the substrate.
  • the glycoluril group may be halogenated with an oxidative halogen compound, such as a hypochlorite, for example aqueous sodium hypochlorite.
  • concentration of chlorine at the surface of the substrate may be measured by iodometry, for example in ppm defining the surface molar concentration of the chlorine.
  • the substrate may be dried.
  • the substrate may be dried by exposing it to a temperature of 20 ° C or more, preferably 30°C or more, more preferably 35 ° C for a period including, but not limited to, 1 hour or more, preferably 4 hours or more.
  • the present invention provides a convenient method for attaching a functional compound such as those containing disease-preventing functional groups to a surface.
  • This method involves providing a compound containing at least one nucleophilic group, such as a compound containing at least two hydrogen atoms attached to one or more nitrogen atoms, and a separate compound containing a cross- linking siloxane precursor group.
  • the compound may contain for example either NH 2 or NH 3 + or two or more nitrogens of the formula NH x , where x is 1 to 3 and where x is independently selected for each amine functional group. Other groups are of course attached to the NH x as so defined).
  • the compounds are applied to the surface of the substrate at the same time as one another.
  • the surface is then exposed to microwave electromagnetic radiation (preferably substantially at the same time as applying the compounds to the surface of the substrate).
  • the term "compound containing a siloxane precursor cross-linking group” refers to a compound that contains one or more silicon atoms that are in total capable of reaction with at least two nucleophiles.
  • the compound may alternatively be referred to as a silicon-containing compound having two or more leaving groups.
  • the compound is capable of reacting with the surface (whose preferable characteristics are the same as the first aspect), with the glycoluril compound itself and optionally with itself (to form a siloxane polymer).
  • the siloxane precursor cross-linking compound is able to undergo at least two reactions in which nucleophiles displace a leaving group at one or more silicon atom.
  • the compound preferably contains a total of at least two leaving groups. These may append either the same silicon atom or, if the compound contains more than one silicon atoms, these may append different silicon atoms. With at least two leaving groups, the compound is able to both react with a surface and also with a glycoluril- containing compound. As such, its function is to cross-link the surface to the glycoluril- containing compound.
  • the leaving groups appended to the silicon atom(s) in this second aspect are the same as in the first aspect.
  • the terms "leaving group” and “nucleophile” are well known in the art (see, for example, “Guidebook to Mechanism in Organic Chemistry” (1986) by Peter Sykes). Thus, “leaving group” refers to a moiety that is easily displaced and replaced by a nucleophile. Common leaving groups include moieties that are relatively stable once displaced and may include be moieties that are stabilised in the presence of acidic or basic condition.
  • R is hydrogen or an alkyl, preferably a C1 to C6 alkyl, more preferably a C1 or a C2 alkyl, such as methyl or ethyl.
  • Other leaving groups include amines, alkylamines (C1 to C6 preferably), carboxylates (C1 to C6 preferably), alkylamides (C1 to C6 preferably), halides, azides and thiocyanates. In the above alkyl group chain length ranges, C1 and C2 alkyl groups are preferred.
  • the leaving groups may be silicon-X 3 functional groups, wherein X 3 is hydrogen, a halogen, O-alkyl, O-heteroalkyl, OH, NH 2 , NH-alkyl, NH- heteroalkyl, N(alkyl)(alkyl), N(alkyl)(heteroalkyl) or N(heteroalkyl)(heteroalkyl).
  • X 3 is hydrogen, a halogen, O-alkyl, O-heteroalkyl, OH, NH 2 , NH-alkyl, NH- heteroalkyl, N(alkyl)(alkyl), N(alkyl)(heteroalkyl) or N(heteroalkyl)(heteroalkyl).
  • siloxane polymers themselves may be suitable.
  • the siloxane precursor cross-linking compound has a total of at least three leaving groups appending one or more silicon atom(s). This is so that they may undergo three separate reactions, namely reaction with a surface, reaction with the glycoluril- containing compound and self-reaction to form a organised array.
  • the siloxane precursor cross-linking compound may comprise at least four leaving groups appending one or more silicon atoms. Examples of suitable siloxane precursor cross-linking compounds include compounds having the chemical structure:
  • R 16 and R 17 are independently selected from hydrogen, an alkyl group or a heteroalkyl group, preferably a C 1 to C 6 alkyl, more preferably, a Ci or C 2 alkyl, such as methyl or ethyl;
  • the polymer defined above preferably includes electron donor groups on at least some of its monomers. These electron donor groups may be substituents on Ri 8 and / or Ri 9 in formulas (6) and (7) above. Electron donor groups include, but are not limited to, hydroxyl, amine, sulfhydryl and carboxyl.
  • X the number of repeating units in the polymer, may be any appropriate number. X may be 2 to 10000, preferably 2 to 1000.
  • Ri 8 and / or R 19 are substituted with one or more halogens.
  • the halogens are located at the distal end of the group(s) from the silicon.
  • the halogen is chlorine.
  • the siloxane precursor cross-linking compound is a compound having the following structure:
  • R 20 , R 211 R 22 and R 23 are independently selected from hydrogen, an alkyl group or a heteroalkyl group, preferably a Ci to C ⁇ alkyl, more preferably, a Ci or C 2 alkyl, such as methyl or ethyl.
  • Ri 6 , R 1 7, Ri 8 and Ri 9 are the same and may preferably be chosen to be methyl or ethyl. In particular, these compounds may be particularly effective in forming a resilient coating having functionality.
  • the siloxane precursor cross-linking compound may be selected from orthosilicic acid, a tetraalkoxysilane, preferably tetramethoxysilane or tetraethoxysilane, a tetraacyloxysilane, preferably tetraformyloxysilane or tetraacetoxysilane, tetraminosilane, or a tetra(alkylamino)silane.
  • tetraethylorthosilicate preferably tetraethylorthosilicate
  • a functional compound may be provided that contains at least two hydrogen atoms attached to one or more nitrogen atoms.
  • the "compound containing at least two hydrogen atoms attached to one or more nitrogen atoms” includes within its scope compounds in which one or more of the hydrogens are replaced by a protecting group so long as the compound contains at least one hydrogen attached to a nitrogen atom.
  • the protecting group is de-protected exposing another hydrogen attached to a nitrogen atom.
  • the hydrogen may be being protected by being replaced by a halogen (for example chlorine or bromine), in which case there is no need to de-protect the nitrogen because it already has some disease- preventing properties.
  • a halogen for example chlorine or bromine
  • the compound does not contain a silicon atom.
  • the known disease-control properties of a N-halogen group may be taken advantage of. While the functional compound may be selected and certain processing conditions (e.g. microwave irradiation during / shortly after exposure of the surface to the functional compound and the siloxane precursor) may be used to render a surface effective against toxins, the N-halogen group is known also to be effective against pathogens. Accordingly, this aspect is not restricted to the specifically-selected groups of the first aspect of the invention but is much more widely applicable to disease-control coatings and other functional coatings.
  • the "compound containing at least two hydrogen atoms attached to one or more nitrogen atoms” may be cyclic or acyclic. Preferably, it is cyclic. Preferably, the compound contains a functional group selected from the group consisting of hydantoin, imidazolidinone, glycoluril, isocyanurate and triazinedione.
  • the hydantoin functional group preferably has the following chemical formula:
  • N-Halogen preferably N-Cl or N-Br.
  • Protecting groups are well-known in the art (see, for example, the book “Protective Groups in Organic Synthesis” by Greene et a/.).
  • X 1 and X 2 are independently-selected optionally-substituted heteroatoms (i.e. atoms other than carbon).
  • X 1 and / or X 2 may be oxygen, nitrogen or sulphur. If either X 1 or X 2 is nitrogen, the nitrogen is substituted with a third substituent, i.e. X 1 and / or X 2 have the chemical formula NR 7 .
  • this third substituent (R 7 ) is hydrogen.
  • R 7 (or any other optional substituent) may be OH, O-alkyl, O-heteroalkyl, alkyl or heteroalkyl.
  • R 24 and R 25 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl and a siloxane monolayer precursor- containing group, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl).
  • the imidazlidinone functional group preferably has the following chemical formula (it can have two forms):
  • N-Halogen preferably N-Cl or N-Br.
  • Protecting groups are well-known in the art (see, for example, the book “Protective Groups in Organic Synthesis” by Greene et al.).
  • X 1 is an optionally-substituted heteroatom (i.e. an atom other than carbon).
  • X 1 may be oxygen, nitrogen or sulphur. If X 1 is nitrogen, the nitrogen is substituted with a third substituent, i.e. X 1 has the chemical formula NR 7 .
  • this third substituent (R 7 ) is hydrogen.
  • R 7 (or any other optional substituent) may be OH, O-alkyl, O-heteroalkyl, alkyl or heteroalkyl.
  • R 24 , R 25 , R 26 and R 17 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl and a siloxane monolayer precursor-containing group, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl).
  • the isocyanurate functional group preferably has the following formula:
  • N-Halogen preferably N-Cl or N-Br.
  • Protecting groups are well-known in the art (see, for example, the book “Protective Groups in Organic Synthesis” by Greene et a/.).
  • X 1 , X 2 and X 3 are independently-selected optionally-substituted heteroatoms (i.e. atoms other than carbon).
  • Xi and / or X 2 may be oxygen, nitrogen or sulphur. If either X 1 or X 2 is nitrogen, the nitrogen is substituted with a third substituent, i.e. X 1 , X 2 and / or X 3 have the chemical formula NR 7 .
  • this third substituent (R 7 ) is hydrogen.
  • R 7 (or any other optional substituent) may be OH, O-alkyl, O-heteroalkyl, alkyl or heteroalkyl.
  • R 24 is selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl and a siloxane monolayer precursor-containing group, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl).
  • R 24 may be a protective group for NH.
  • the triazinedione functional group preferably has the following formula:
  • N-Halogen preferably N-Cl or N-Br.
  • Protecting groups are well-known in the art (see, for example, the book “Protective Groups in Organic Synthesis” by Greene et a/.).
  • X 1 and X 2 are independently-selected optionally-substituted heteroatoms (i.e. atoms other than carbon).
  • X 1 and / or X 2 may be oxygen, nitrogen or sulphur. If either X 1 or X 2 is nitrogen, the nitrogen is substituted with a third substituent, i.e. X 1 and / or X 2 have the chemical formula NR 7 .
  • this third substituent (R 7 ) is hydrogen.
  • R 7 (or any other optional substituent) may be OH, O-alkyl, O-heteroalkyl, alkyl or heteroalkyl.
  • R 24 , R 25 and R 26 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl and a siloxane monolayer precursor- containing group, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl).
  • R 24 may be a protecting group for NH.
  • the compound containing at least two hydrogen atoms is a glycoluril compound.
  • the free NH is able to react with the siloxane precursor cross- linking compound.
  • a group appending the glycoluril functional group may be capable of reacting with the siloxane precursor cross-linking compound. If one or more halogen atoms are not appended to any of the other atoms in the glycoluril functional group, then preferably the glycoluril functional group contains at least two NH groups (the second one is then activated to become NCI).
  • the glycoluril compound of this second aspect has the following chemical formula:
  • X 1 and X 2 are independently-selected optionally-substituted heteroatoms (i.e. atoms other than carbon).
  • Xi and / or X 2 may be oxygen, nitrogen or sulphur. If either X 1 or X 2 is nitrogen, the nitrogen is substituted with a third substituent, i.e. X 1 and / or X 2 have the chemical formula NR 7 .
  • this third substituent (R 7 ) is hydrogen.
  • R 7 (or any other optional substituent) may be OH, O-alkyl, O-heteroalkyl, alkyl or heteroalkyl.
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl and heteroalkyl.
  • R 5 and R 6 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl and a siloxane monolayer precursor-containing group, OH 1 O-alkyl, O- heteroalkyl, NH 2 , NH(alkyl), NH(heteroalkyl), N(alkyl)(alkyl), N(alkyl)(heteroalkyl) and N(heteroalkyl)(heteroalkyl). At least one of R 1 , R 2 , R 3 and R 4 is hydrogen.
  • R 1 , R 2 , R 3 and R 4 are a halogen (preferably chlorine or bromine) or a protecting group for NH, then preferably at least two of Ri, R 2 , R 3 and R 4 are hydrogen.
  • Protecting groups are well-known in the art (see, for example, the book “Protective Groups in Organic Synthesis” by Greene et a/.).
  • this method forms a resilient coating on the surface of a substrate.
  • the functional compound is linked directly to the silicon centre rather than through a linker group and the possible in situ formation of the coating allows the functional group to be more resiliently attached to the surface.
  • This resilient coating may be further enhanced by treating the substrate with microwaves (the specifics of which are the same as those described in the first aspect of the invention), such as substantially at the same time as applying the compounds to the surface.
  • the functional compound is selected from a compound containing a functional group selected from the group consisting of glycoluril, isocyanurate and triazinedione.
  • these functional groups contain three or more aliphatic nitrogens containing potentially free hydrogens, thus allowing each functional group to be attached to a surface through more than one silicon atom while exhibiting disease-control properties.
  • a more resilient disease-control coating may be formed.
  • N-halogen groups for example N-Cl or N-Br groups.
  • the present invention provides a substrate having a coating deposited according to the first or second aspect.
  • depositing a coating using microwaves rather than heat results in a physical change in the properties of the coating. Therefore, a coating formed while being irradiated by microwaves is physically different from a coating formed simply by heating.
  • the third aspect provides a substrate having compounds as defined in either the first or second aspects attached to, and / or organised into an array on the surface of the substrate.
  • the present invention provides a novel glycoluril derivative that is especially adapted for use in the first and second aspects of the present invention.
  • This glycoluril derivative has the chemical structure: wherein:
  • R 1 , R 2 , R 3 and R 4 , R 5 and R 6 are independently selected from hydrogen, the halogens (preferably chlorine or bromine), alkyl, heteroalkyl, a group containing a siloxane monolayer precursor, OH, O-alkyl, O-heteroalkyl, NH 2 , NH(alkyl),
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a group containing a siloxane monolayer precursor.
  • This compound has been found by the inventor to be particularly effective when attached to a surface and used to deactivate toxins.
  • R 1 to R 6 are the same for this aspect as for the first and third aspects of the present invention.
  • the inventor has found that the use of a siloxane monolayer precursor to attach a glycoluril functional group to a surface has certain disadvantages. Therefore, the inventor has sought new ways of forming disease-preventing coatings containing a glycoluril functional group on a surface. Accordingly, in a fifth aspect, the invention provides certain precursors for forming a coating containing a glycoluril functional group that is effective against toxins. These precursors have the following chemical structure:
  • R 1 to R 6 are as defined previously. At least one or Ri to R 6 is a group containing a vinyl group, an imide, an acrylate, an alkene, an epoxide or an alkyl halide.
  • These precursors are more convenient to prepare than their siloxane monolayer precursor equivalents.
  • These compounds may be prepared by the person skilled in the art using the techniques of the art.
  • the present invention provides a method for forming a coating on a substrate by applying the compound (7) to a surface and allowing it to form a coating on the surface.
  • the coating may be preferably formed or cured by heat or microwaves.
  • the present invention provides a substrate coated with a coating formed by the sixth aspect of the present invention.
  • the present invention also provides the use of the coatings described above in the deactivation of toxins.
  • These coatings may be formed from, for example, a compound containing a glycoluril functional group and a siloxane monolayer precursor group or compound (7).
  • the synthesis of glycoluril crosslinked aluminium oxide may be achieved where Boehmite aluminium oxide is wetted with a basic water-alcohol solution containing glycoluril and tetraethylorthosilicate. The boehmite may then be irradiated with microwaves for three one minute intervals, washed thoroughly, and allowed to dry.
  • the product may be chlorinated via 30 minute wash in 0.5% aqueous sodium hypochlorite, washed thoroughly, and dried overnight at room temperature under vacuum.
  • the presence of oxidative chlorine may be confirmed via colorimetric reaction with potassium iodide and starch indicator solution.
  • chlorinated glycoluril crosslinked boehmite The ability of the chlorinated glycoluril crosslinked boehmite to deactivate toxins was confirmed via standard enzyme inhibition studies using three representative toxin simulants, nitrobenzene nitroreductase, lysozyme, and laccase. In each case the chlorinated glycoluril boehmite significantly (greater than 99.9% reduction in enzyme activity in all cases) inhibited the enzyme activity compared to controls.
  • the controls used were untreated boehmite, treated unchlorinated glycoluril boehmite, and the representative enzyme solution without a solid matrix.
  • hydantoinylated aluminium oxide may be confirmed by wetting boehmite aluminium oxide with a basic water-alcohol solution containing 1- hydroxymethyl-5,5-dimethyl hydantoin and tetraethylorthosilicate.
  • the boehmite may then be irradiated with microwaves for three one minute intervals, washed thoroughly, and allowed to dry.
  • the product from this may be titrated via iodometry. Test results may be found to contain 8 ppm of active, oxidative chlorine. From previous experiments it is believed that 2 ppm or greater of active chlorine is suitable to inactivate toxins, with a greater amount of active chlorine resulting in a greater efficacy.

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Abstract

La présente invention concerne un procédé de formation d’un revêtement antiparasitaire sur un substrat, le procédé consistant à fournir un composé contenant au moins deux atomes d’hydrogène fixés à un atome d’azote ou plus et un composé contenant un groupe précurseur de réticulation à base de siloxane, et à appliquer les composés sur la surface.
EP09777997A 2008-08-20 2009-08-20 Enduction pour le contrôle des maladies Withdrawn EP2348837A2 (fr)

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US9033708P 2008-08-20 2008-08-20
US12/362,890 US8815351B2 (en) 2005-09-15 2009-01-30 Method for attachment of silicon-containing compounds to a surface and for synthesis of hypervalent silicon-compounds
PCT/EP2009/006034 WO2010020415A2 (fr) 2008-08-20 2009-08-20 Revêtements antiparasitaires

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US6969769B2 (en) * 2002-06-14 2005-11-29 Vanson Halosource, Inc. N-halamine siloxanes for use in biocidal coatings and materials
US7384626B2 (en) * 2004-08-31 2008-06-10 Triton Systems, Inc. Functionalized dendritic polymers for the capture and neutralization of biological and chemical agents
US8815351B2 (en) * 2005-09-15 2014-08-26 The United States Of America As Represented By The Secretary Of The Air Force Method for attachment of silicon-containing compounds to a surface and for synthesis of hypervalent silicon-compounds
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