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WO2012113068A1 - Émulsions d'élastomères durcissables par radicaux libres - Google Patents

Émulsions d'élastomères durcissables par radicaux libres Download PDF

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Publication number
WO2012113068A1
WO2012113068A1 PCT/CA2012/000170 CA2012000170W WO2012113068A1 WO 2012113068 A1 WO2012113068 A1 WO 2012113068A1 CA 2012000170 W CA2012000170 W CA 2012000170W WO 2012113068 A1 WO2012113068 A1 WO 2012113068A1
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emulsion
free
macromonomer
surfactant
radical initiator
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Scott J. Parent
Ralph A. Whitney
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Queens University at Kingston
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Queens University at Kingston
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • 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

Definitions

  • the present invention relates to emulsions that provide cross-linked polymeric films and coatings via free-radical initiated curing techniques.
  • Poly(isobutylene-co-isoprene), or IIR is a synthetic elastomer commonly known as "butyl rubber” that has been prepared since the 1940's through random cationic
  • IIR isobutylene with small amounts of isoprene (1-2 mole %).
  • IIR possesses superior gas impermeability, excellent thermal stability, good resistance to ozone oxidation, exceptional dampening characteristics, and extended fatigue resistance.
  • butyl rubber is cross-linked to generate thermoset articles with greatly improved modulus, creep resistance and tensile properties.
  • sulfur and metal containing byproducts are not desired in the cross-linked product, free-radical initiated cures are used.
  • Many halogen-free elastomers are readily cured by currently available peroxide- initiated crosslinking techniques, but butyl rubber is not (Loan, L. D. Pure Appl. Chem. 1972, 30, 173-180; Loan, L.D. Rubber Chem. Technol. 1967, 40, 149-176).
  • Emulsions composed of a dispersed phase of butyl rubber (IIR) particles (i.e., non- derivatized butyl rubber) in a continuous phase of water are commercially available, and provide an aqueous delivery system for depositing IIR films and coatings.
  • IIR butyl rubber
  • These emulsions typically include one or more surfactants that serve as ionic/steric stabilizers, which hinder particle coalescence and improve emulsion stability against coagulation.
  • surfactants that serve as ionic/steric stabilizers
  • the surfactants needed to stabilize the IIR emulsion can compromise adhesion of the final polymer film to the intended substrate, particularly when the film is exposed to water during product use. • These surfactants are not polymer bound, and can be leached out of the final product into contacting fluids, resulting in their contamination.
  • Butyl rubber provides poor adhesive strength relative to more polar elastomers.
  • Relatively inefficient sulphur-based vulcanization technology is therefore needed, which presents contamination problems associated with residual curatives and requires relatively high cure temperatures that can complicate the film crosslinking process.
  • Butyl rubber is not an anti-microbial material.
  • butyl rubber-derived emulsion technology that can provide films and coatings that provide superior adhesion to other surfaces, and can be cured by free-radical cross-linking methods.
  • An aspect of the invention provides an emulsion comprising an aqueous phase, a dispersed macromonomer phase, and a surfactant.
  • the macromonomer comprises azolium ionomer.
  • Certain embodiments of this aspect further comprise filler.
  • Some embodiments of this aspect comprise free-radical initiator, cross-linking coagent, reinforcing filler, non-reinforcing filler, viscosity modifier, processing aid, antioxidant, ultraviolet radiation stabilizer, wax, oil, or a combination thereof.
  • Some embodiments of this aspect comprise other additives.
  • the surfactant comprises vinyl alkyl azolium halide salt, a salt of itaconate half ester, a copolymer comprising an isobutylene-rich polymer backbone with pendant polyether chains covalently bound through itaconate diester, or a combination thereof.
  • An aspect of the invention provides a method of making a macromonomer emulsion comprising, in any order: adding a surfactant to an aqueous liquid; and dispersing macromonomer in the aqueous liquid to form an emulsion.
  • the surfactant comprises at least one moiety that is suitable to participate in crosslinking reactions.
  • Another aspect of the invention provides a cross-linked polymeric film prepared by spreading the emulsion of the above aspect and exposing the spread emulsion to a free- radical initiator.
  • the film is antimicrobial.
  • Some embodiments of this aspect further comprise filler, free-radical initiator, reinforcing filler, non- reinforcing filler, viscosity modifier, processing aid, antioxidant, ultraviolet radiation stabilizer, wax, oil, or a combination thereof.
  • a method of making a cross-linked polymer film comprising: spreading an emulsion comprising surfactant, dispersed macromonomer, and a continuous aqueous phase on a substrate; reacting the macromonomer with a free-radical initiator; and allowing cross-linking reactions to occur so that cross-linked polymeric film is obained. Certain embodiments of this aspect further comprise allowing time for the spread emulsion to dry prior to reacting the macromonomer with a free-radical initiator.
  • the free- radical initiator is: a chemical free-radical initiator, a photoinitiator, heat, heat in the presence of oxygen, thermo-mechanical initiating means, electron bombardment, irradiation, high- shear mixing, photolysis (photo-initiation), ultraviolet light, electron beam radiation, radiation bombardment, or a combination thereof.
  • the chemical free-radical initiator comprises an organic peroxide, a hydroperoxide, bicumene, dicumyl peroxide, di-t-butyl peroxide, an azo-based initiator, homolysis of an organic peroxide, or a combination thereof.
  • kits comprising: an emulsion of macromonomer dispersed in an aqueous liquid in the presence of surfactant; optionally, a free-radical initiator; and instructions for use of the kit comprising directions to form a cross- linked polymeric film from the emulsion.
  • the instructions comprise printed material, text or symbols provided on an electronic-readable medium, directions to an internet web site, electronic mail, or a combination thereof.
  • aspects of the present invention provide emulsions comprising isobutylene-rich elastomers that are capable of being cured using free-radical initiation methods (such elastomers are known herein as "macromonomers").
  • Such macromonomers may additionally provide a moiety that fulfills a function other than crosslinking; such moieties are known herein as "functional moieties”.
  • An example of a functional moiety is a moiety that binds silaceous fillers.
  • Macromonomers bearing functional moieties are known herein as "functional macromonomers”.
  • Other aspects of the present invention provide methods of making emulsions of macromonomers, and methods of cross-linking macromonomer emulsions to form cured polymeric films using free-radical crosslinking techniques.
  • azole is a cyclic five-membered heteroaromatic compound having one nitrogen atom and at least one other non-carbon atom of either nitrogen, sulfur, or oxygen.
  • examples of azoles described herein include imidazoles, pyrazoles, oxazoles, thiazoles, and triazoles.
  • azolium ionomer refers to a polymer backbone and a plurality of azolium cations that are covalently-bound to the backbone in a pendant position, and a plurality of anionic counterions associated with the plurality of cations.
  • the anions may be halo, or may be a variety of other moieties.
  • phase means the phase in a two or more phase mixture that is interconnected in a uninterrupted fashion.
  • dispersed phase means the phase in a two or more phase mixture which has separate and unconnected globules, droplets, particles or bubbles.
  • curing refers to the formation of covalent bonds that link one polymer chain to another, thereby altering the physical properties of the material.
  • emulsion means a suspension of small globules of one liquid in a second liquid with which the first liquid is not miscible. Some molecules act at the many interfaces throughout the emulsion as surface active agents (called surfactants or emulsifiers) and reduce energy needed to keep these liquids apart.
  • surfactants or emulsifiers
  • radical generating technique means a method of creating free-radicals, including the use of chemical initiators, photo-initiation, radiation
  • free-radical curing and “free-radical polymerizable” mean able to polymerize when initiated by a free-radical initiator.
  • free- radical curing means crosslinking or curing that is initiated by free-radical initiators, which include chemical initiators, photoinitiators or radiation bombardment.
  • free-radical curing means cross-linking that is initiated by a radical generating technique.
  • radical generating technique means a method of creating free-radicals, including the use of chemical initiators, photo-initiation, radiation bombardment, thermo-mechanical processes, oxidation reactions or other techniques known to those skilled in the art.
  • the terms "functional group” and "FG” refers to a moiety including but not limited to aliphatic, aryl, phenyl, halogen, silane, alkoxysilane, phenolic, aryl alcohol, ether, thioether, aldehyde, ester, thioester, dithioester, carbonate, carbamate, amide, imide, nitrile, imine, enamine, olefin, vinyl, alkyne, phosphate, phosphonate, phosphonium, sulfate, sulfonate, sulfoxide, ammonium, imidazolium, pyridinium, thiazolium or mixtures thereof.
  • the term "functionality" is a chemical moiety that performs a function following ionomer preparation.
  • a pendant group on an polymer that includes an -Si(OMe) 3 moiety can perform the function of binding to siliceous fillers.
  • Non-limiting examples of functionalities include: silane, alkoxysilane, siloxane, alcohol, epoxide, ether, carbonyl, carboxylic acid, carboxylate, aldehyde, ester, anhydride, carbonate, tertiary amine, imine, amide, carbamate, urea, maleimide, nitrile, olefin, acrylate, methacrylate, itaconate, styrenic, borane, borate, thiol, thioether, sulfate, sulfonate, sulfonium, sulfite, thioester, dithioester, halogen, peroxide, hydroperoxide, phosphate, phosphonate, phosphine, phosphate, phosphonium, alkyl, and aryl.
  • Halogenated polymer as used herein includes polymers comprising non- electrophilic mers that do not react with the azoles described herein, and electrophilic halogen- comprising mers that do react with nitrogen nucleophiles.
  • the non-electrophilic mer composition within a halogenated polymer is not particularly restricted, and may comprise any polymerized olefin monomer.
  • olefin monomer is has a broad meaning and encompasses a-olefin monomers, diolefin monomers and polymerizable monomers comprising at least one olefin.
  • halogenated polymer comprises BUR, CIIR, BIMS, chlorinated polyethylene, or a combination thereof.
  • MR means poly(isobutylene-co-isoprene) containing less than 4 mole% isoprene, which is a synthetic elastomer commonly known as butyl rubber.
  • BUR means brominated butyl rubber.
  • CIIR means chlorinated butyl rubber.
  • BIMS means brominated poly(isobutylene-co-methylstyrene).
  • macromonomer means a polymer with pendant groups bearing moieties that are capable of polymerization under free-radical curing.
  • pendant group means a moiety that is attached to a polymer backbone.
  • polymer backbone As used herein, the terms “polymer backbone”, “main chain”, and “PB” mean the main chain of a polymer to which pendant group is attached. As used is structures shown herein, a connection to “Polymer” or “PB” is not meant to be limiting, and may, for example, be a bond to polymer backbone.
  • substrate means a material or object, it usually refers to an object or surface that is desired to be coated, and may include glass, mylar, plastic, mineral, metal, composite, wood, construction materials and ceramic surfaces.
  • An aspect of the invention provides an emulsion comprising a continuous aqueous phase, a dispersed macromonomer phase, and a surfactant.
  • a macromonomer is an elastomer that is capable of being cured using free-radical initiation methods.
  • the macromonomer is an azolium ionomer and has azolium pendant groups.
  • Certain aspects of the invention provide an emulsion that further comprises fillers or other additives.
  • cured polymeric film or coating that results from reacting the emulsion with a free-radical initiator has advantageous characteristics. Such characteristics may include superior adhesion, antimicrobial properties, or a combination thereof.
  • Such antimicrobial films and coatings have use in childcare facilities, hospitals, spas, health clubs, etc as they can be applied to exercise equipment, shower stalls, handheld devices, shared tools, toilets, etc. Aspects of the invention provide films and coatings with improved adhesion, UV resistance, antioxidant properties, etc. Such coatings have use as adhesive liners in tanks, and containers for housing and/or transporting liquids, for coating pipes, and for many surfaces where a free-radical curable isobutylene-rich elastomer can be applied by, for example, spraying, dipping, wiping, or immersing.
  • the macromonomer is an azolium ionomer with a general formula (1) shown below, comprising: a polymer backbone, a plurality of covalently-bound, pendant azolium cations, and a plurality of anions associated with azolium cations to form ion pairs:
  • Polymer- Azolium X ⁇ where " Azolium* " represents a polymer-bound azolium cation, " X " represents an anion associated with the azolium cation, and "Polymer” is a macromolecule to which the azolium cation is covalently attached. Notably, there are a plurality of anionic counterions to balance the charge of the crosslinking cationic azolium moieties. As those with skill in the art of the invention will recognize, a macromonomer may have many pendant groups attached.
  • a singular pendant group may be described to represent a plurality of pendant cations and associated anions.
  • azole is a cyclic five-membered heteroaromatic compound having one nitrogen atom and at least one other non-carbon atom of either nitrogen, sulfur, or oxygen.
  • azole is an imidazole, which is a compound of formula (1 ) shown below:
  • R 1 , R 3 and R 4 are independently hydrogen, silane, a substituted or unsubstituted Ci to about Ci 6 aliphatic group, a substituted or unsubstituted d to about C 6 aryl group, or a combination thereof, and optionally bear a functionality;
  • R 2 is non-hydrogen, and is independently a substituted or unsubstituted Ci to about C 16 aliphatic group, a substituted or unsubstituted d to about C 16 aryl group, or a combination thereof, and optionally bears a functionality;
  • R 2 is a substituted or unsubstituted olefin.
  • Non-limiting examples of compounds of formula (1 ) include the following imidazoles: N-butyl imidazole, N-(trimethylsilyl)imidazole, N-decyl-2-methylimidazole, and N- hydroxyethyl imid ively:
  • compounds of formula (1) include: N-(3- trimethoxysilylpropyl) imidazole, N-vinylimidazole, 2-(imidazol-1-yl)ethyl 2-methyl-2- propenoate, and 1-butylbenzimidazole, whose structures are illustrated below, respectively:
  • the azole is a pyrazole of formula (2) shown below:
  • R , R 3 and R 4 are independently hydrogen, silane, a substituted or unsubstituted Ci to about C 16 aliphatic group, a substituted or unsubstituted C-, to about C 16 aryl group, or a combination thereof, and optionally bear a functionality;
  • R 2 is a substituted or unsubstituted to about C 16 aliphatic group, a substituted or unsubstituted d to about C 16 aryl group, or a combination thereof, optionally bearss a functionality; optionally any combination of R ⁇ R 2 , R 3 and R 4 together with the azole ring atoms to which they are bonded, to form a cyclic structure.
  • R 2 is a substituted or unsubstituted olefin.
  • Non-limiting examples of compounds of formula (2) include: N-(3- trimethoxysilylpropyl) pyrazole and N-vinylpyrazole, whose structures are illustrated below, respectively:
  • the azole is a compound of formula (3) shown below:
  • X is a heteroatom that is non-nitrogen, e.g., sulphur, oxygen
  • R ⁇ R 2 and R 3 are independently hydrogen, silane, a substituted or unsubstituted to about Ci 6 aliphatic group, a substituted or unsubstituted Ci to about C 6 aryl group, or a combination thereof, and optionally bear a functionality (e.g., substituents may bear a functionality); and
  • R 2 and R 3 taken together with the azole ring atoms to which they are bonded, form a cyclic structure.
  • Non-limiting examples of azoles of formula (3) include: oxazole and benzothiazole, whose structures are illustrated below, respectively:
  • azole is a compound of formula (4), known as a triazole, with three nitrogen atoms at the 1 ,2,3- or 1 ,2,4- positions of the heteroaromatic ring, as illustrated below:
  • R 1 is a substituted or unsubstituted Ci to about C16 aliphatic group, a substituted or unsubstituted Ci to about Ci 6 aryl group, or a combination thereof, and optionally bearss a functionality moiety (e.g., substituents may bear a functionality);
  • R 2 and R 3 are independently hydrogen, silane, a substituted or unsubstituted Ci to about Ci6 aliphatic group, a substituted or unsubstituted Ci to about Ci 6 aryl group, or a combination thereof, and optionally bear a functionality moiety (e.g., substituents may bear a functionality);
  • any combination of R 1 , R 2 , and R 3 taken together with the azole ring atoms to which they are bonded, form a cyclic moiety.
  • R 1 is a substituted or unsubstituted olefin.
  • Non-limiting examples of triazoles of formula (4) include: l-vinyl-1 ,2,4-triazole, and 1-methyl-1 ,2,3-triazole, whose below, respectively:
  • the macromolecule to which the azolium cation is bound is not particularly restricted.
  • the macromolecule comprises a random distribution of isobutylene mers and isoprene mers.
  • the macromolecule comprises a random distribution of isobutylene mers and para-methylstyrene mers.
  • a non-limiting example of this embodiment is a BIIR-
  • the macromonomer comprises a polymer backbone and pendant group with the following structure
  • R 1 , R 2 , R 3 , R 4 are independently hydrogen, substituted or unsubstituted C-i to about C 12 aliphatic group, substituted or unsubstituted aryl, or combinations thereof.
  • the variable n can range from 1 to 5. In some embodiments n is 1 to 3. In still other embodiments, n is 1.
  • X is oxygen, N-H, or N-R where R is a substituted or unsubstituted Ci to about C 12 aliphatic group, substituted or unsubstituted aryl, or combinations thereof.
  • the functionality within the group FG, defined hereinabove, is not particularly restricted, and is in the purview of those skilled in the art.
  • functionality within the group FG include aliphatic, aryl, phenyl, halogen, silane, alkoxysilane, phenolic, aryl alcohol, ether, thioether, aldhehyde, ester, thioester, dithioester, carbonate, carbamate, amide, imide, nitrile, imine, enamine, olefin, vinyl, alkyne, phosphate, phosphonate, phosphonium, sulfate, sulfonate, sulfoxide, ammonium, imidazolium, pyridinium, thiazolium, and mixtures thereof.
  • Surfactant is not particularly restricted and can be cationic, anionic or non-ionic.
  • the amount of surfactant or emulsifier employed can vary from about 2 to 20 weight percent based on the weight of macromonomer present.
  • Some embodiments use surfactant that bears at least one moiety that can react in crosslinking reactions so that the surfactant participates in cross-linking reactions and is bound in the cured product. Such surfactants will not leach from the product.
  • the surfactant is a vinyl alkyl azolium bromide salt, a non-limiting example of which is illustrated below:
  • the surfactant is the salt of itaconate half ester, examples of which are illustrated below:
  • the surfactant is a copolymer comprising an isobutylene-rich polymer backbone with pendant polyether chains that are bound covalently through
  • filler such as carbon black, precipitated silica, talc, clay, glass fibres, polymeric fibres, crystalline organic compounds, finely divided minerals and finely divided inorganic materials can improve the physical properties of polymers.
  • the amount of filler is between 10 wt% and 60 wt%.
  • filler content is between 20 and 45 wt%.
  • Suitable fillers for use in the present invention comprise particles of a mineral, such as, for example, silica, silicates, clay (such as bentonite), gypsum, alumina, titanium dioxide, talc and the like, as well as mixtures thereof. Further examples of suitable fillers include:
  • silicas prepared, e.g., by the precipitation of silicate solutions or the flame hydrolysis of silicon halides, with specific surface areas of 5 to 1000, preferably 20 to 400 m 2 /g (BET specific surface area), and with primary particle sizes of 10 to 400 nm;
  • the silicas can optionally also be present as mixed oxides with other metal oxides such as Al, Mg, Ca, Ba, Zn, Zr, and Ti;
  • magnesium silicate or calcium silicate with BET specific surface areas of 20 to 400 m 2 /g and primary particle diameters of 10 to 400 nm;
  • natural silicates such as kaolin and other naturally occurring silica
  • natural clays such as montmorillonite, and their ion-exchanged derivatives such as tetraalkylammonium ion exchanged clays
  • glass fibers glass fiber products (matting, extrudates), and glass microspheres
  • metal oxides such as zinc oxide, calcium oxide, magnesium oxide and aluminum oxide
  • metal carbonates such as magnesium carbonate, calcium carbonate and zinc
  • metal hydroxides e.g., aluminum hydroxide and magnesium hydroxide
  • Mineral fillers as described hereinabove, can also be used alone or in combination with known non-mineral fillers, such as:
  • carbon blacks are preferably prepared by the lamp black, furnace black or gas black process and have BET specific surface areas of 20 to 200 m 2 /g, for example, SAF, ISAF, HAF, FEF, and GPF carbon blacks;
  • rubber gels preferably those based on polybutadiene, butadiene/styrene
  • nano-scale filler such as exfoliated clay platelets, sub-micron particles of carbon black, and sub-micron particles of siliceous fillers such as silica can improve the physical properties of polymers, in particular the impermeability, stiffness and abrasion resistance of the material.
  • the amount of nano-scale filler is between 0.5 wt% and 30 wt%.
  • nano-scale filler content is from about 2 to about 10 wt%.
  • fillers as described hereinabove, are included during the preparation processes of azolium ionomer, and are part of the emulsions so they form part of the cured polymeric film or coating.
  • the method of dispersing filler into the uncured formulation is not particularly restricted, and selection of an appropriate mixing device is within the purview of one skilled in the art.
  • the amount of filler added to the uncured formulation ranges from 2- 60 percent of the total mixture weight. More preferably, the filler content is between 4 and 35 wt%.
  • emulsions include other additives that improve physical properties, chemical properties, and cost.
  • additives can include, but are not restricted to, free-radical initiators, cross-linking coagents, reinforcing fillers, non-reinforcing fillers, viscosity modifiers, processing aids, antioxidants, ultraviolet radiation stabilizers, waxes, oils, and the like.
  • additives known to those skilled in the art of the invention are included in the azolium ionomer preparation process to improve material properties. For example, provision of antioxidants such as phenolics and amines can improve oxidative stability of the material.
  • typical antioxidant amounts are 10-1000 ppm.
  • Anti-ozone and UV-stabilizing compounds can be added to improve weathering characteristics.
  • process aids such as, e.g., tackifiers, waxes, oils, and soaps can improve the processing properties and cost of a polymer emulsion formulation.
  • cured and uncured azolium ionomers provide enhanced adhesion.
  • Adhesion of a polymer to solid surfaces is an important physical property that leads to formation of composite materials.
  • most polyolefins exhibit only moderate adhesion to glass, mylar, plastic, mineral, metal and ceramic surfaces and, as a result, have deficiencies when used in composite applications.
  • Introduction of an ionic moiety to a polymer composition is expected to improve adhesive properties over its non-ionic parent material, owing to the strength of ion-dipole interactions between ionomers and solid surfaces.
  • azolium ionomers (cured in films and uncured in emulsions) reduce a population of and/or prevent accumulation of organisms, including bacteria, algae, fungi, mollusks, and/or arthropods.
  • organisms including bacteria, algae, fungi, mollusks, and/or arthropods.
  • the inventors suggest that the ion pairs may impart antimicrobial properties that are not observed in typical halogenated polymers.
  • thermoset azolium ionomer for example: Gram-negative bacteria - Salmonella, Shigella, Neisseria
  • gonorrhoeae Neisseria meningitidis, Haemophilus influenzae, Escherichia coli, Klebsiella, Pseudomonas aeruginosa.
  • Gram-positive bacteria Bacillus, Listeria, Staphylococcus, Streptococcus, Enterococcus, Clostridium, Epulopiscium, Sarcina, Mycoplasma,
  • Spiroplasma Ureaplasma, Lactobacillus, Corynebacterium, Propionibacterium, Gardnerella, Frankia, Streptomyces, Actinomyces, and Nocardia.
  • Algae Chlorophyta, Rhodophyta, Glaucophyta, Chlorarachniophytes, Euglenids, Heterokonts, Haptophyta, Cryptomonads, Dinoflagellates.
  • Fungi Alternaria, Aspergillus, Basidiomycetes, Botrytis, Candida albicans, Cephalosporium, Cheatomium, Cladosporium, Cuvalaria, Drechslera, Epicoccum, Fusarium, Geotrichum, Helminthosporium, Humicola, Monilia, Neuspoa, Nigrospora, Penicillium, Phoma, Pullularia, Rhizophus, Rhodotorula, Scopulariopsis, Stemphylium, Trichoderma, Unocladium and Verticillum. Method of macromonomer preparation
  • Macromonomers have been prepared with a variety of moieties that crosslink under free-radical conditions.
  • Non-limiting examples of certain macromonomer embodiments include acrylate ester macromonomers, maleimido-ester macromonomer, IIR-g-dodecyl maleate, and IMS-g-aminosilane itaconate. Syntheses for these example macromonomers are included in the Working Examples.
  • An aspect of the invention provides macromonomers bearing azolium ionomers. Syntheses of certain azolium macromonomers are included in the Working Examples. Briefly, to prepare such macromonomers, halogenated polymers and at least one azole are mixed to form a mixture. Optionally, the mixture can comprise other additives (e.g., filler) as described herein. This preparation method can be conducted both in the absence or in the presence of solvent.
  • Solvent-free azolium ionomer preparations can be carried out to obtain various conversion amounts converting azole and halogenated electrophile to azolium salts.
  • the amount of conversion of azoles to azolium salts is preferably maximized, such that isolation of residual azole from the product is not required. If residual azole remains in the ionomer product, it may be left in the material or removed by heating, placing under vacuum, or heating and placing under vaccuum.
  • Amount of conversion of halogenated electrophile to azolium salt may be selected based on the desired azolium ionomer composition. Where ion pair concentrations are to be maximized, desired halogenated electrophile conversion is 100%.
  • halogenated electrophile is desired within the azolium ionomer, this conversion can be reduced. Such residual may be desired, for example, if halogenated electrophile is needed in the azolium ionomer for other reactions such as vulcanization.
  • halogenated polymers In the presence of solvent, halogenated polymers, one or more azoles, and optionally, other additives, are mixed in the presence of a solvent that is suitable for dissolving the halogenated polymer.
  • a solvent that is suitable for dissolving the halogenated polymer.
  • suitable solvents include toluene, hexane, tetrahydrofuran, xylene and mixtures thereof.
  • the rate of these solvent-borne reactions is dependent on temperature, and these processes are typically carried out from about 60°C to about 160°C.
  • the reaction is conducted at a pressure that is sufficient to maintain the polymer mixture in a liquid state using a suitably equipped pressure vessel.
  • azole and halogenated electrophiie conversions can be independently controlled to provide a desired azolium ionomer product composition.
  • Recovery of product from solution is possible by addition of ionomer product solution to a solvent that does not dissolve the product, thereby leading to precipitation of azolium ionomer from solution.
  • ionomer product cement can be subjected to steam stripping to remove solvent, leaving a crumb that can be dried using conventional methods.
  • a non-limiting example of a method of making a macromonomer emulsion comprises dissolving the macromonomer in a suitable nonaqueous solvent, and dispersing the resulting mixture in an aqueous surfactant solution. Non-aqueous solvent is then removed under reduced partial pressure and/or at elevated temperature.
  • An aspect of the invention provides a cross-linked film comprising surfactants, and optionally fillers and/or other additives described hereinabove, and a macromonomer that has been cured by exposure to a radical generating technique.
  • the method of generating this film from a macromonomer emulsion is not particularly restricted, and may comprise spraying, brushing, or rolling the emulsion on a surface and allowing the resulting coating to dry by water evaporation.
  • the resulting film is then exposed to a free-radical generating technique to cross-link the coating, yielding a thermoset product.
  • the radical generating technique may comprise activating the initiator by heat, light, radiation, or combinations thereof.
  • a macromonomer (0.5 g) comprising a IIR backbone and 0.15 mmole/g of pendant vinyl imidazoiium groups was dissolved in a mixture of hexanes (4.5 g) and hexanoi (0.12g).
  • the resulting mixture was dispersed in an aqueous solution of Brij 35 surfactant (0.05g) (available from Acros Organics, NJ, USA) in water (5 g) using a sonicating probe (model CV33 Vibra Cell by Sonics, Sonics & Materials, Inc., Newtown, CT, USA) to yield an emulsion.
  • the resulting emulsion was stable for 24 hours.
  • 1-vinyl-3-n-decyl-imidazoiium bromide is used as surfactant in place of Brij 35 in the above example.
  • 1-vinyl-3-n-decyl-imidazolium bromide is advantageous since it is involved in crosslinking reactions, so the cured product does not leach surfactant.
  • An ionomer (0.5 g) comprising a IIR backbone and 0.15 mmole/g of pendant butyl imidazoiium groups was dissolved in a mixture of hexanes (4.3 g) and hexanoi (0.23g). The resulting mixture was dispersed in an aqueous solution of 1-vinyl-3-n-decyl-imidazolium bromide (0.2 g) surfactant in water (5g) using a sonicating probe. The resulting emulsion was placed in a rotary evaporator (R110 by BOchi, Flawil, Switzerland) at room temperature and placed under reduced pressure for several hours to remove the organic solvent, yielding an emulsion.
  • a rotary evaporator R110 by BOchi, Flawil, Switzerland
  • 1-vinyl-3-n-decyl-imidazolium bromide surfactant was a synthesized according to the procedure in Bottino, F.A. ef a/. "Polystyrene-Clay Nanocomposites Prepared with
  • a macromonomer (1 g) comprising a IIR backbone bearing 0. 5 mmole/g of pendant butyl imidazoiium groups and dicumyl peroxide (0.005 g) free-radical initiator is dissolved in a mixture of hexanes (10 g) and hexanoi (0.5 g). The resulting mixture is dispersed in an aqueous solution of 1-vinyl-3-n-decyl-imidazolium bromide (0.1 g) surfactant in water (30g) using a sonicating probe. The resulting emulsion is placed in a rotary evaporator at room temperature and placed under reduced pressure (17 inches water, 0.6 bar) for two hours to remove the organic solvent.
  • the resulting macromonomer emulsion is used to coat a glass slide, and the water is allowed to evaporate prior to heating the film to 140 °C for 30 min to activate the initiator.
  • the resulting cured macromonomer film has substantially no extractable surfactant, provides excellent adhesion to the glass substrate, and exhibits antimicrobial activity.
  • This example illustrates the synthesis of an azolium ionomer under solvent-free conditions.
  • BUR 40 g, 6.0 mmol of allylic bromide
  • 1-butylimidazole 0.816 g, 6.57 mmole
  • Samples taken at specified time intervals were analyzed by 1 H N R.
  • Imidazolium bromide contents were quantified by integration of the following allylic resonances: ⁇ 4.86 (E-IIR- ImidazoliumBr, s); ⁇ 4.95 (Z-IIR-lmidazoliumBr, s).
  • Example 5 Solvent-borne preparation of an azolium ionomer from BUR and 1 -butyl imidazole
  • This example illustrates the synthesis of an azolium ionomer by reaction of BUR with 1-butylimidazole under solvent-borne conditions.
  • a solution of BUR (10.0 g, 1.5 mmol) and 1-butylimidazole (1.12 g, 9.0 mmol) in toluene (104 mL) was maintained at 100 ⁇ 2 °C for 6 hours under a nitrogen atmosphere. Aliquots (-0.5 mL) withdrawn at time intervals were added to excess acetone to isolate the polymeric reaction product, which was dried under vacuum and characterized by 1 H NMR spectroscopy as described in the previous example. Displacement of bromide from BUR by 1 -butyl imidazole proceeds to full conversion of allylic bromide to imidazolium bromide.
  • This example illustrates the synthesis of an azolium ionomer by reaction of CIIR with N-butylimidazole under solvent-borne conditions.
  • a 10 wt% xylene solution of chlorinated butyl rubber comprising 0.02 mmole of exomethylene allylic chloride per gram of polymer and 0.12 mmole of Cl-Me alllylic per gram of polymer was heated to 135°C with 6 molar equivalents of N-butylimidazole for 56 minutes.
  • the reaction product was isolated by precipitation from acetone, dried under vacuum, and analyzed by 1 H-NMR, revealing an N- butylimidazolium chloride content of 0.03 mmole/g.
  • Example 7 Synthesis of acrylate ester macromonomers
  • BUR was transformed into acrylate ester macromonomers (IIR-g-AA) as follows.
  • BUR (2 g, as received or isomerized) was dissolved in toluene (8 g) along with BHT (0.02 g) and the required amounts of nudeophile/phase transfer catalyst (0.19 g Bu4NAcrylate or 0.063 g KAcrylate+0.013 g Bu4NBr) under a nitrogen atmosphere, and heated to 85°C using an oil bath. Samples withdrawn at intervals were precipitated from acetone and dried in vacuo at room temperature.
  • IIR-g-AA materials for rheological testing were prepared on 15 g scale from as received BUR for 3 hours to ensure complete allylic bromide consumption.
  • BUR (11 g) and Bu4NBr (0.53 g, 1.65 mmol) were dissolved in toluene (100 g) and heated to 85°C for 180 min.
  • Bu4Ncarboxylate salt (1.73 g, 3.3 mmol) was added before heating the reaction mixture to 85°C for 60 min.
  • the esterification product was isolated by precipitation from excess acetone, purified by dissolution/precipitation using

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Abstract

La présente invention concerne des émulsions d'élastomères durcissables par radicaux libres qui peuvent être appliquées sur des substrats et durcies dans des conditions radicalaires, formant des films polymères. Certains de ces films sont antimicrobiens. Les émulsions selon l'invention comprennent une phase aqueuse continue, une phase d'élastomère durcissable par radicaux libres dispersée, et un tensio-actif. Lesdits élastomères ont une chaîne principale riche en isobutylène et des groupes pendants portant des fractions qui subissent des réactions de réticulation dans des conditions radicalaires.
PCT/CA2012/000170 2011-02-23 2012-02-23 Émulsions d'élastomères durcissables par radicaux libres Ceased WO2012113068A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2448437A1 (fr) * 2001-06-05 2002-12-12 Ram Technologies Group, Inc. Emulsions aqueuses de bitume contenant du caoutchouc recycle liquefie ou regenere
CA2653230A1 (fr) * 2008-02-15 2009-08-15 Xerox Corporation Methode d'inversion de phase sans solvant permettant de produire des emulsions de resine
WO2009114788A2 (fr) * 2008-03-14 2009-09-17 Allegiance Corporation Composition de résine à base d’eau et articles fabriqués à partir de cette composition
US7820747B2 (en) * 1998-01-27 2010-10-26 Lord Corporation Method for preparing adhesives from stable butadiene polymer latexes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7820747B2 (en) * 1998-01-27 2010-10-26 Lord Corporation Method for preparing adhesives from stable butadiene polymer latexes
CA2448437A1 (fr) * 2001-06-05 2002-12-12 Ram Technologies Group, Inc. Emulsions aqueuses de bitume contenant du caoutchouc recycle liquefie ou regenere
CA2653230A1 (fr) * 2008-02-15 2009-08-15 Xerox Corporation Methode d'inversion de phase sans solvant permettant de produire des emulsions de resine
WO2009114788A2 (fr) * 2008-03-14 2009-09-17 Allegiance Corporation Composition de résine à base d’eau et articles fabriqués à partir de cette composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PORTER, ANTHONY M J: "Imidazolium Ionomer Derivatives of Polv(isobutylene-co-isoprene)", MSC THESIS QUEEN'S UNIVERSITY, October 2010 (2010-10-01), KINGSTON, ON *

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