WO2022118246A1 - Agent ignifuge encapsulé et compositions et procédés associés - Google Patents

Agent ignifuge encapsulé et compositions et procédés associés Download PDF

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Publication number
WO2022118246A1
WO2022118246A1 PCT/IB2021/061242 IB2021061242W WO2022118246A1 WO 2022118246 A1 WO2022118246 A1 WO 2022118246A1 IB 2021061242 W IB2021061242 W IB 2021061242W WO 2022118246 A1 WO2022118246 A1 WO 2022118246A1
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Prior art keywords
particles
fire
weight
composition
multivalent
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PCT/IB2021/061242
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English (en)
Inventor
Hassan Sahouani
Michael D. ZENNER
Ryan K. Mckenney
Dillon S. GENTEKOS
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3M Innovative Properties Company
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Publication of WO2022118246A1 publication Critical patent/WO2022118246A1/fr

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons

Definitions

  • the present disclosure provides particles useful as fire retardants.
  • Cores of fire retardants are encapsulated by inorganic shells.
  • the inorganic shells can be useful, for example, for preventing premature transition to the gas phase. They can also be useful, for example, for improving compatibility of fire-retardant particles with the composition that includes it and can help protect a substrate onto which such a composition is applied.
  • the particles of the present disclosure have been found useful, for example, for reducing the flammability of thin films.
  • the present disclosure provides particles that include cores of fire-retardant particles and shells of an inorganic salt encapsulating the cores.
  • the inorganic salt includes a multivalent cation and a multivalent anion.
  • the present disclosure provides a composition of an adhesive with the aforementioned particles dispersed therein.
  • the present disclosure provides a tape including the aforementioned composition disposed on a backing. In another aspect, the present disclosure provides an article including flexible ductwork including the aforementioned composition.
  • the present disclosure provides a process of making the aforementioned composition, the process includes combining the particles and the adhesive.
  • the present disclosure provides the process of making the particles.
  • the process includes combining the fire-retardant particles and an aqueous solution of a salt of a monovalent cation and the multivalent anion, removing water to provide fire retardant particles coated with the salt of the monovalent cation and the multivalent anion, dispersing the coated fire retardant particles in a solution of a salt including the multivalent cation and a monovalent anion in a solvent, and obtaining the particles having the cores of fire retardant particles and the shells of the inorganic salt of the multivalent cation and the multivalent anion encapsulating the cores.
  • phrases “comprises at least one of followed by a list refers to comprising any one of the items in the list and any combination of two or more items in the list.
  • the phrase “at least one of followed by a list refers to any one of the items in the list or any combination of two or more items in the list.
  • curable refers to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably.
  • a cured or crosslinked polymer is generally characterized by insolubility but may be swellable in the presence of an appropriate solvent.
  • polymer or polymeric will be understood to include polymers, copolymers (e.g., polymers formed using two or more different monomers), oligomers, and combinations thereof, as well as blends of polymers, oligomers, and/or copolymers.
  • alkyl group and the prefix “alk-” are inclusive of both straight chain and branched chain groups and of cyclic groups. In some embodiments, alkyl groups have up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons) unless otherwise specified. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms. Terminal “alkenyl” groups have at least 3 carbon atoms.
  • Arylalkylene refers to an “alkylene” moiety to which an aryl group is attached.
  • Alkylarylene refers to an "arylene” moiety to which an alkyl group is attached.
  • aryl and “arylene” as used herein include carbocyclic aromatic rings or ring systems, for example, having 1, 2, or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring optionally substituted by up to five substituents including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl), alkoxy having up to 4 carbon atoms, halo (i.e., fluoro, chloro, bromo or iodo), hydroxy, or nitro groups.
  • heteroatom e.g., O, S, or N
  • substituents including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl), alkoxy having up to 4 carbon atoms, halo (i.e., fluoro, chloro, bromo or iodo), hydroxy, or nitro groups.
  • aryl groups include phenyl, naphthyl, biphenyl, fluorenyl as well as furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl.
  • organophosphinate means a chemical species according to the general formula R2P(O)(OR), where each R group is selected independently from organic groups.
  • organophosphine oxide means a chemical species according to the general formula R3P(O), where each R group is selected independently from organic groups.
  • PSA pressure sensitive adhesive
  • materials having the following properties: a) tacky surface, b) the ability to adhere with no more than finger pressure, c) the ability to adhere without activation by any energy source, d) sufficient ability to hold onto the intended adherend, and preferably e) sufficient cohesive strength to be removed cleanly from the adherend; which materials typically meet the Dahlquist criterion of having a storage modulus at 1 Hz and room temperature of less than 0.3 MPa.
  • Particles of the present disclosure include cores of fire-retardant particles.
  • the fire-retardant particles are typically solid and not soluble in water.
  • a variety of fire-retardant particles that are solid and not soluble in water can be useful. Any class of fire retardants may be useful, including halogenated compounds (e.g., brominated or chlorinated), inorganic fire retardants (e.g., aluminum hydroxides and magnesium hydroxides), nitrogen-containing compounds (e.g., melamine -based compounds), spumific compounds, boron-containing compounds, and phosphorous-containing compounds.
  • halogenated compounds e.g., brominated or chlorinated
  • inorganic fire retardants e.g., aluminum hydroxides and magnesium hydroxides
  • nitrogen-containing compounds e.g., melamine -based compounds
  • spumific compounds boron-containing compounds, and phosphorous-containing compounds.
  • Suitable fire retardants may include decabromo-diphenylether, tetrabromo bisphenol A (TBA), octabromoether (BDDP), decabromo-diphenyl ethane, tetrabromoether, bromopolystyrene, hexabromocyclododecane (HBCD), chlorinated paraffin, chlorinated polyethylene (CPE), decabromo diphenylether, octabromo diphenyl ether, pentabromo diphenyl ether, 2,2-di(chloromethyl)cyclopropane (V-6), ammonium chloride, brominated epoxy resin, dibromo-neopentyl-glycol (DBNPG), dibromo-neopentyl- glycolphosphate, dibromo-neopentyl-glycol phosphate cyanamide, hexabromocyclododecane (HBCD), tribro
  • fire-retardant particles are phosphorous-containing fire-retardant particles.
  • phosphorous-containing fire-retardant particle as used herein means that the fire-retardant particle includes at least one phosphorous atom. Thus, this element may also be called a “phosphorous atom-containing fire-retardant particle”.
  • the fire-retardant particle comprises at least one of a phosphate, a polyphosphate, a phosphonate, a phosphinate, a phosphazene, a phosphine, or a phosphine oxide.
  • Useful phosphorous-containing flame retardants include red phosphorus; tri(2- chloroethyl)phosphate (TCEP); tri(2-chloropropyl)phosphate (TCPP); tri(2,3-dichloropropyl)phosphate (TDCP); mono-ammonium phosphate; di-ammonium phosphate; triphenylphosphate; those obtained from Clariant Corporation, Charlotte, N.C., under the trade designations “EXOLIT OP” in various grades and (e.g., “EXOLIT OP 1311”, “EXOLIT OP 1312 Ml”, “EXOLIT OP 935”, and “EXOLIT OP 945”) and “EXOLIT RP”; ammoniumpolyphosphate (APP); melamine phosphate (MP); tri(2,3- dibromopropyl)phosphate; tetrakis(hydroxymethyl)phosphoniumchloride (THPC); cyclic phosphate derivatives; phosphorus-containing polyo
  • the fire-retardant particles comprise at least one of an organophosphine oxide or an organophosphinate.
  • Suitable organic substituents “R” of the organophosphine oxides or organophosphinates include alkyl, aryl, and arylalkylenyl.
  • each R is independently a substituted or unsubstituted C1-C12 linear, branched, or cyclic alkyl group (e.g., ethyl, n- propyl, isopropyl, n-butyl, and isobutyl), or a C1-C12 aryl or arylalkylenyl group (e.g., substituted or unsubstituted phenyl or benzyl).
  • the fire-retardant particles comprise at least one of aluminum diethyl phosphinate or triphenyl phosphine oxide. In some embodiments, the fire-retardant particles comprise triphenyl phosphine oxide.
  • Particles of the present disclosure comprise an inorganic salt comprising a multivalent cation and a multivalent anion encapsulating the fire-retardant particles described above in any of their embodiments.
  • the term “encapsulating” refers to at least a major portion (that is, greater than 50%) of the surface of a fire-retardant particle is covered by the inorganic salt. In some embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% of the surface of the fire-retardant particle is covered by the inorganic salt. In some embodiments, the inorganic salt completed surrounds the surface of the inorganic particle. A variety of multivalent cations can be useful for the inorganic salt.
  • the multivalent cation comprises at least one of calcium, barium, magnesium, zinc, aluminum, or strontium. In some embodiments, the multivalent cation is an alkaline earth metal. In some embodiments, the multivalent cation is calcium. In some embodiments, the multivalent anion comprises at least one of sulfate, phosphate, or carbonate. In some embodiments, the multivalent anion comprises carbonate. In some embodiments, the inorganic salt comprises at least one of magnesium carbonate, calcium carbonate, zinc carbonate, calcium sulfate, magnesium sulfate, or calcium phosphate. In some embodiments, the inorganic salt comprises at least one of calcium carbonate, calcium phosphate, or calcium sulfate.
  • Fire-retardant properties of the particles of the present disclosure can be enhanced by gas produced by the inorganic shell while burning.
  • Phosphate and carbonate salts can be useful for producing gases, for example.
  • the inorganic salt is a carbonate salt, which produces carbon dioxide.
  • the inorganic salt comprises calcium carbonate.
  • the present disclosure also comprises a process of making the particles described above in any of their embodiments.
  • the process includes combining the fire-retardant particles including any of the solid, water-insoluble particles described above, and an aqueous solution of an inorganic salt of a monovalent cation and the multivalent anion.
  • the multivalent anion can be any of those described above, in some embodiments, sulfate, phosphate, or carbonate.
  • the monovalent cation can be an alkali metal cation or ammonium.
  • the monovalent cation comprises at least one of sodium, potassium, or ammonium.
  • the inorganic salt of the monovalent cation and the multivalent anion is sodium carbonate, potassium carbonate, or ammonium carbonate.
  • the fire-retardant particles can be mixed with the aqueous solution in an amount up to 20% by weight, up to 15% by weight, and up to 10% by weight, or at least 1% by weight, at least 2% by weight, or at least 3% by weight, based on the total weight of the fire-retardant particles and the aqueous solution.
  • the fire-retardant particles are present with the aqueous solution in an amount from 1% to 20% by weight, 1% to 15% by weight, 2% to 10% by weight, or 3% to 10% by weight, based on the total weight of the fire-retardant particles and the aqueous solution.
  • the inorganic salt of a monovalent cation and the multivalent anion can be dissolved in the aqueous solution in an amount up to 20% by weight, up to 15% by weight, and up to 10% by weight, or at least 1% by weight, at least 2% by weight, or at least 3% by weight, based on the total weight of the fire-retardant particles and the aqueous solution.
  • the inorganic salt of a monovalent cation and the multivalent anion is in the aqueous solution in an amount from 1% to 20% by weight, 1% to 15% by weight, 2% to 10% by weight, or 3% to 10% by weight, based on the total weight of the fire-retardant particles and the aqueous solution.
  • the fire-retardant particles and the aqueous solution can be mixed at room temperature.
  • the aqueous solution further comprises a dispersant.
  • Suitable dispersants include anionic surfactants (e.g., sulfates, sulfonates, phosphates, carboxylates, and sulfates of polyethoxylated derivatives of straight or branched chain aliphatic alcohols and carboxylic acids), cationic surfactants (e.g., quaternary ammonium salts), amphoteric surfactants (e.g., sultaines, betaines, and sulfobetaines), and nonionic surfactants.
  • the dispersant is a nonionic surfactant.
  • Suitable nonionic surfactants include alkyl polyglucosides (e.g., obtained under the trade designation “APG 325”, from BASF SE, Ludwigshafen, Germany), alkyl glucosides (e.g., blend of decyl and undecyl glucoside), fatty amine ethoxylates, fatty alcohol ethoxylates, fatty acid alkanolamides, castor oil ethoxylates, alcohol ethoxylates/propoxylates, and combinations thereof.
  • alkyl polyglucosides e.g., obtained under the trade designation “APG 325”, from BASF SE, Ludwigshafen, Germany
  • alkyl glucosides e.g., blend of decyl and undecyl glucoside
  • fatty amine ethoxylates e.g., fatty alcohol ethoxylates
  • fatty acid alkanolamides e.g., castor oil ethoxylates
  • the dispersant may be present in the aqueous solution in any suitable amount to keep the fire- retardant particles dispersed in the aqueous solution. In some embodiments, the dispersant is present in a range from 0.5% to 10% by weight, 0.5% to 8% by weight, or 1% to 5% by weight, based on the weight of the fire-retardant particles.
  • the aqueous solution further comprises a monovalent anion.
  • the monovalent anion can be, in some embodiments, hydrogen sulfate, dihydrogen phosphate, or bicarbonate.
  • the monovalent anion can be added to the aqueous solution using a further inorganic salt which has a monovalent cation and the monovalent anion.
  • the monovalent cation can be an alkali metal cation or ammonium.
  • the monovalent cation comprises at least one of sodium, potassium, or ammonium.
  • the inorganic salt of the monovalent cation and the monovalent anion is sodium bicarbonate, potassium bicarbonate, or ammonium bicarbonate.
  • the inorganic salt of a monovalent cation and the monovalent anion can be dissolved in the aqueous solution in an amount up to 20% by weight, up to 15% by weight, and up to 10% by weight, or at least 1% by weight, at least 2% by weight, or at least 3% by weight, based on the total weight of the fire-retardant particles and the aqueous solution.
  • the inorganic salt of a monovalent cation and the monovalent anion is in the aqueous solution in an amount from 1% to 20% by weight, 1% to 15% by weight, 2% to 10% by weight, or 3% to 10% by weight, based on the total weight of the fire-retardant particles and the aqueous solution.
  • the process of the present disclosure includes removing water to provide fire-retardant particles coated with the salt of the monovalent cation and the multivalent anion.
  • Removing water can be carried out by any suitable method, for example, filtering, evaporation, centrifugation, or a combination thereof.
  • removing water includes centrifugation of the reaction mixture and discarding the supernatant liquid.
  • the process of the present disclosure further includes dispersing the coated fire-retardant particles in a solution of a salt comprising the multivalent cation and a monovalent anion in a solvent.
  • the multivalent cation can be any of those described above, for example, at least one of calcium, barium, magnesium, zinc, aluminum, or strontium.
  • the multivalent cation is an alkaline earth metal.
  • the multivalent cation is calcium.
  • Suitable monovalent anions include halides (e.g., chloride, bromide, and iodide), acetate, and combinations thereof.
  • the monovalent anion is chloride.
  • the salt comprising the multivalent cation and a monovalent anion is calcium chloride.
  • the salt of a multivalent cation and the monovalent anion can be dissolved in the solvent in an amount up to 20% by weight, up to 15% by weight, and up to 10% by weight, or at least 1% by weight, at least 2% by weight, or at least 5% by weight, based on the total weight of the fire-retardant particles and the aqueous solution.
  • the salt of a multivalent cation and the monovalent anion is in the solvent in an amount from 1% to 20% by weight, 1% to 15% by weight, 5% to 15% by weight, or 5% to 10% by weight, based on the total weight of the solution (that is, salt in solvent).
  • the solvent can comprise at least one of organic solvent or water.
  • Suitable organic solvents include aliphatic alcohols (e.g., methanol, ethanol, and isopropanol); ketones (e.g., acetone, 2-butanone, and 2- methyl-4-pentanone); esters (e.g., ethyl acetate, butyl acetate, and methyl formate); ethers (e.g., diethyl ether, diisopropyl ether, methyl t-butyl ether, 2-methoxypropanol, and dipropyleneglycol monomethylether (DPM)); and combinations thereof
  • the organic solvent is methanol, ethanol, isopropanol, or a mixture thereof.
  • the organic solvent is isopropanol.
  • the solvent is water. Conveniently,
  • Isolating the fire-retardant particles can be carried out, for example, by removing the solvent after treatment with the solution of multivalent cation and monovalent anion.
  • Removing solvent can be carried out by any suitable method, for example, filtering, evaporation, centrifugation, or a combination thereof.
  • removing solvent includes centrifugation of the reaction mixture and discarding the supernatant liquid.
  • the particles of the present disclosure can optionally be washed (e.g., with distilled water) and dried at ambient pressure or reduced pressure.
  • the particles can have a range of useful sizes.
  • the particles have a median particle size (D50) in a range from 0. 1 micrometer to 200 micrometers or more.
  • the median size is also called the D50 size, where 50 percent by volume of the particles in the distribution are smaller than the indicated size.
  • the median particle size is at least 0.1 micrometer, at least 0.5 micrometer, or at least 1 micrometer.
  • the median particle size of the particles is up to 250 micrometers, 200 micrometers, or 150 micrometers.
  • the median particle size can be determined by scanning electron microscopy.
  • the median particle size refers to the largest dimension of the particles.
  • Particle sizes of the fire-retardant particles can be adjusted, if desired, by milling (e.g., ball milling, stamp milling, or jet milling). Milling can be carried out dry or wet (that is, in the absence or presence of solvent, respectively). Typically, milling is carried out before the fire-retardant particles are encapsulated with the inorganic salt having the multivalent cation and the multivalent anion.
  • milling e.g., ball milling, stamp milling, or jet milling. Milling can be carried out dry or wet (that is, in the absence or presence of solvent, respectively). Typically, milling is carried out before the fire-retardant particles are encapsulated with the inorganic salt having the multivalent cation and the multivalent anion.
  • Particles of the present disclosure can be useful in many materials in a wide variety of industries.
  • flame retardants can be found in furnishings (e.g., foams and fabrics), electronics (e.g., electrical wire and cable sheathing, potting compounds, computers, telephones, televisions, and household appliances), construction materials (e.g., electrical wire and cable sheathing, flexible ductwork for heating, ventilation, and air conditioning (HVAC) construction, and insulation), and transportation (e.g., interior and exterior parts of automobiles, planes, and trains and HVAC construction).
  • Particles of the present disclosure can be included in foams, sealants, and adhesives (e.g., structural adhesives and pressure-sensitive adhesives) and extruded into plastics.
  • the present disclosure provides a composition including a polymeric material (e.g., a plastic, rubber, thermoplastic elastomer, or thermoset) and the particles of the present disclosure.
  • the particles of the present disclosure can be dispersed within the composition.
  • the composition can be a foam, sealant, adhesive, or plastic, for example, made from a wide variety of polymers such as polyolefins (polypropylene, polyethylene, high density polyethylene, blends of polypropylene), polyamide 6 (PA6), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), PC/ABS blends, polyvinyl chloride (PVC), polyamide (PA), polyurethane (PUR), thermoplastic elastomers (TPE), polyoxymethylene (POM), polystyrene, poly (methyl) methacrylate (PMMA), and combinations thereof.
  • polymers such as polyolefins (polypropylene, polyethylene, high density polyethylene,
  • the composition of the present disclosure comprises an adhesive with the particles of the present disclosure dispersed therein.
  • the adhesive is a PSA.
  • PSAs include natural rubber-, synthetic rubber-, rubber modified asphalt (bitumen)-, acrylic-, block copolymer-, silicone-, polyisobutylene-, polyvinyl ether-, polybutadiene-, and urea-based PSAs and combinations thereof. These PSAs can be prepared, for example, as described in Adhesion and Adhesives Technology, Alphonsus V.
  • the adhesive is selected to be a solventless or hot melt adhesive.
  • solvent-based adhesives or water-based adhesives may be used.
  • suitable adhesives include radiation-cured adhesives (e.g., ultraviolet (UV) radiation or electron-beam cured (co)polymers resulting from polymerizable monomers or oligomers).
  • the composition of the present disclosure in some embodiments, the adhesive composition
  • the particles are present in an amount in a range from 10 percent by weight to 70 percent by weight, based on the total weight of the composition. In some embodiments, the particles are present in an amount of 15 percent by weight to 50 percent by weight, 18 percent by weight to 50 percent by weight, 20 percent by weight to 50 percent by weight, 25 percent by weight to 50 percent by weight, 50 percent by weight to 70 percent by weight, or 60 percent by weight to 70 percent by weight based on the total weight of the composition.
  • the composition of the present disclosure (in some embodiments, the adhesive composition) further comprises fire-retardant particles having no shell of an inorganic salt.
  • the fire-retardant particles can be any of those described above in any of their embodiments.
  • the combined particles of the present disclosure and the fire-retardant particles having no shell of an inorganic salt are present in an amount in a range from 10 percent by weight to 70 percent by weight, based on the total weight of the composition.
  • the combined particles of the present disclosure and the fire-retardant particles having no shell of an inorganic salt are present in an amount of 15 percent by weight to 50 percent by weight, 18 percent by weight to 50 percent by weight, 20 percent by weight to 50 percent by weight, 25 percent by weight to 50 percent by weight, 50 percent by weight to 70 percent by weight, or 60 percent by weight to 70 percent by weight based on the total weight of the composition.
  • Suitable adhesives for the composition of the present disclosure may contain (co)polymers such as butyl rubber, ethylene propylene diene (EPDM) rubber, styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene butadiene (SB), styrene-ethylene-butadiene-styrene (SEBS), and ethylene/vinylacetate (EVA).
  • Tackifying resins which generally refer to materials that are compatible with the elastomer and have a number average molecular weight of up to 10,000 grams per mole, are typically added to these elastomers.
  • Useful tackifying resins can have a softening point of at least 70 °C as determined using a ring and ball apparatus and a glass transition temperature of at least -30 °C as measured by differential scanning calorimetry.
  • the tackifying resin comprises at least one of rosin, a polyterpene (e.g., those based on a-pinene, -pinene, or limonene), an aliphatic hydrocarbon resin (e.g., those based on cis- or trans-piperylene, isoprene, 2-methyl-but-2-ene, cyclopentadiene, dicyclopentadiene, or combinations thereof), an aromatic resin (e.g.
  • tackifying resins may be hydrogenated (e.g., partially or completely).
  • Natural and petroleum waxes, oil, and bitumen may be useful as additives to the pressure sensitive adhesive composition.
  • PSAs useful in the composition of the present disclosure are acrylic PSAs.
  • the term "acrylic” or “acrylate” includes compounds having at least one of acrylic or methacrylic groups.
  • Useful acrylic PSAs can be made, for example, by combining at least two different monomers. Examples of suitable first monomers include 2-methylbutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, lauryl acrylate, n-decyl acrylate, 4-methyl-2-pentyl acrylate, isoamyl acrylate, sec-butyl acrylate, isononyl acrylate, and methacrylates of the foregoing acrylates.
  • Suitable first monomers include mixtures of at least two or at least three structural isomers of a secondary alkyl (meth)acrylate of Formula (I): wherein R 1 and R 2 are each independently a Ci to C30 saturated linear alkyl group, in which the sum of the number of carbons in R 1 and R 2 is 7 to 31, and R 3 is H or CH3.
  • the sum of the number of carbons in R 1 and R 2 can be, in some embodiments, 7 to 27, 7 to 25, 7 to 21, 7 to 17, 7 to 11, or 7.
  • suitable second monomers useful for preparing acrylic PSAs include a (meth)acrylic acid (e.g., acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid), a (meth)acrylamide (e.g., acrylamide, methacrylamide, N-ethyl acrylamide, N-hydroxy ethyl acrylamide, N-octyl acrylamide, N-t-butyl acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-ethyl-N-dihydroxyethyl acrylamide, and methacrylamides of the foregoing acrylamides), a (meth)acrylate (e.g., 2-hydroxyethyl acrylate or methacrylate, cyclohexyl acrylate, t-butyl acrylate, isobomyl acrylate, and methacrylates of the foregoing acrylates),
  • Acrylic PSAs may also be made by including cross-linking agents in the formulation.
  • cross-linking agents include copolymerizable polyfimctional ethylenically unsaturated monomers (e.g., 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and 1,2-ethylene glycol diacrylate); ethylenically unsaturated compounds which in the excited state are capable of abstracting hydrogen (e.g., acrylated benzophenones such as described in U.S. Pat. No.
  • the first monomer is used in an amount of 80 parts to 100 parts by weight (pbw) based on a total weight of 100 parts of copolymer
  • a second monomer as described above is used in an amount of 0-20 pbw based on a total weight of 100 parts of copolymer.
  • the crosslinking agent can be used in an amount of 0.005 to 2 weight percent based on the combined weight of the monomers, for example from about 0.01 to about 0.5 percent by weight or from about 0.05 to 0.15 percent by weight.
  • the acrylic PSAs useful for practicing the present disclosure can be prepared, for example, in solvent or by a solvent free, bulk, free-radical polymerization process (e.g., using heat, electron-beam radiation, or ultraviolet radiation).
  • a polymerization initiator e.g., a photoinitiator or a thermal initiator.
  • the polymerization initiator is used in an amount effective to facilitate polymerization of the monomers (e.g., 0.1 part to about 5.0 parts or 0.2 part to about 1.0 part by weight, based on 100 parts of the total monomer content).
  • a useful solvent-free polymerization method is disclosed in U.S. Pat. No. 4,379,201 (Heilmann et al.).
  • Solvent-based adhesives may contain ingredients such as those listed above, dissolved or dispersed in a solvent vehicle.
  • the solvent can include any of the organic solvents described above.
  • Water-based adhesives would normally be based on emulsions of (co)polymeric materials. Suitable (co)polymeric materials include vinyl acetate and (meth)acrylic homopolymers and copolymers.
  • the present disclosure provides a process of making the composition including the adhesive described above with the particles described above in any of their embodiments.
  • the process comprises combining the particles and the adhesive.
  • Combining the particles and the adhesive can include combining a dispersion of the particles and a dispersion of the adhesive.
  • the dispersions of the particles and the adhesives can be water-based or solvent-based.
  • the solvent can include any of the organic solvents described above.
  • the dispersion of the particles and the dispersion of the adhesive are water-based.
  • Combining a dispersion of the particles and a dispersion of the adhesive can be carried out in the presence of a dispersant, including any of the surfactants described above.
  • the dispersant is a nonionic surfactant.
  • Suitable nonionic surfactants include alkyl polyglucosides, alkyl glucosides (e.g., blend of decyl and undecyl glucoside), fatty amine ethoxylates, fatty alcohol ethoxylates, fatty acid alkanolamides, castor oil ethoxylates, alcohol ethoxylates/propoxylates, and combinations thereof.
  • the dispersion can be mixed using conventional methods (e.g., shaking or stirring), and the water or solvent can be removed from the composition using conventional methods (e.g., drying at ambient or elevated temperature).
  • the present disclosure provides a tape comprising the composition including the adhesive described above with the particles described above in any of their embodiments disposed on a backing.
  • Useful tapes typically comprise a polymeric fdm or paper backing onto which an adhesive (in some embodiments, pressure sensitive adhesive) is disposed.
  • Polymeric materials suitable as a film for an adhesive article include polyesters; polycarbonates; polyolefins (e.g., polyethylene); ethyl cellulose film; cellulose esters (e.g., cellulose acetate, cellulose acetate butyrate, and cellulose propionate); polyvinylidene chloride-vinyl chloride and/or acrylonitrile polymers such as saran; vinyl chloride polymers (e.g., copolymers of vinyl chloride and vinyl acetate); polyfluoroethylenes (e.g., polytetrafluoroethylene and polytrifluorochloroethylene); polyvinyl alcohol; polyamides such as nylon; polystyrenes such as the copolymers of styrene and isobutylene; regenerated cellulose; benzyl cellulose; cellulose nitrate; gelatin; glycol cellulose; acrylate and methacrylates; urea aldehyde films; polyvinyl
  • the tape comprises a film comprising at least one of polyester, polycarbonate, polyolefin, or acrylic onto which an adhesive is disposed to provide the adhesive surface.
  • the film may include deposited metal layers such as aluminum, silver, and nickel.
  • the tape can include a release liner on the adhesive or a release coating opposite the surface on which the adhesive is disposed.
  • a release liner can be a paper liner or polymer film made, for example, from any of the polymers described above with a release coating on at least one surface.
  • the release coating can be a silicone, fluorochemical, or carbamate coating.
  • composition of the present disclosure may have a thickness of 5 micrometers to 1000 micrometers, 5 micrometers to 500 micrometers, 5 micrometers to 300 micrometers, 5 micrometers to 200 micrometers, 5 micrometers to 100 micrometers, 10 micrometers to 1000 micrometers, 10 micrometers to 500 micrometers, 10 micrometers to 300 micrometers, 10 micrometers to 200 micrometers, or 10 micrometers to 100 micrometers.
  • a ductwork construction useful for HVAC constructions is comprised of an inner core containing a metal coil laminated between layers of clear polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the inner core is then wrapped with fiberglass insulation which is finally wrapped with an outer layer.
  • the outer layer typically includes scrim laminated between a layer of clear PET and metalized PET with thin adhesive layers.
  • TPPO triphenyl phosphine oxide
  • Triphenylphosphine oxide has a boiling point of 360 °C while most frame fronts bum in excess of 1000 °C. Therefore, some fraction of TPPO may escape through evaporation before being ignited by the flame front. This effect may be exacerbated by reducing the particle size of the TPPO due to the relationship between increased surface area and more rapid melting and evaporation.
  • TPPO with a median particle size (D50) of 5 micrometers did not provide fire protection in a construction comprising layers of clear PET, adhesive, scrim, adhesive, metalized PET, in which the adhesive is a PSA made from styrene-butadiene rubber.
  • the construction did not pass the Bum Test described in the Examples, below.
  • the TPPO was replaced with TPPO encapsulated with an inorganic salt comprising a multivalent cation and a multivalent anion, the construction did pass the Bum Test.
  • the inorganic salt shell may prevent volatilization of the TPPO before being ignited in the flame.
  • the present disclosure provides particles comprising: cores of fire-retardant particles; and shells of an inorganic salt comprising a multivalent cation and a multivalent anion encapsulating the cores.
  • the present disclosure provides the particles of the first embodiment, wherein the fire-retardant particles are solid and not water soluble.
  • the present disclosure provides the particles of the first or second embodiment, wherein the multivalent cation comprises at least one of calcium, barium, magnesium, zinc, or aluminum.
  • the present disclosure provides the particles of any one of the first to third embodiments, wherein the multivalent anion comprises at least one of sulfate, phosphate, or carbonate.
  • the present disclosure provides the particles of any one of the first to fourth embodiments, wherein the inorganic salt comprises at least one of calcium carbonate, calcium phosphate, or calcium sulfate.
  • the present disclosure provides the particles of any one of the first to fifth embodiments, wherein the particles contain phosphorous.
  • the present disclosure provides the particles of any one of the first to sixth embodiments, wherein the fire-retardant particles comprise at least one of an organophosphine oxide or an organophosphinate.
  • the present disclosure provides the particles of any one of the first to seventh embodiments, wherein the fire-retardant particles comprise triphenyl phosphine oxide. In a ninth embodiment, the present disclosure provides the particles of any one of the first to eighth embodiments, wherein the particles have an average particle size in a range from 0.1 micrometer to 250 micrometers.
  • the present disclosure provides a composition comprising an adhesive and the particles of any one of the first to ninth embodiments dispersed therein.
  • the present disclosure provides the composition of the tenth embodiment, wherein the adhesive is a pressure sensitive adhesive.
  • the present disclosure provides the composition of the tenth or eleventh embodiment, wherein the particles are present in an amount in a range from 10 percent by weight to 70 percent by weight, based on the total weight of the composition.
  • the present disclosure provides the composition of any one of the tenth to twelfth embodiments, further comprising fire-retardant particles having no shell of an inorganic salt.
  • the present disclosure provides the composition of any one of the tenth to thirteenth embodiments, wherein the adhesive comprises an acrylic polymer.
  • the present disclosure provides the composition of any one of the tenth to thirteenth embodiments, wherein the adhesive comprises a rubber.
  • the present disclosure provides a tape comprising the composition of any one of the tenth to fifteenth embodiments, disposed on a backing.
  • the present disclosure provides a process of making the composition of any one of the tenth to fifteenth embodiments, the process comprising combining the particles and the adhesive.
  • the present disclosure provides the process of the seventeenth embodiment, wherein combining the particles and the adhesive comprises combining a dispersion of the particles and a dispersion of the adhesive.
  • the present disclosure provides the process of the eighteenth embodiment, wherein the dispersion of the particles and the dispersion of the adhesive are water-based.
  • the present disclosure provides an article comprising flexible ductwork comprising the composition of any one of the tenth to fifteenth embodiments.
  • the present disclosure provides a process of making the particles of any one of the first to ninth embodiments, the process comprising: combining the fire-retardant particles and an aqueous solution of an inorganic salt of a monovalent cation and the multivalent anion; removing water to provide fire retardant particles coated with the salt of the monovalent cation and the multivalent anion; dispersing the coated fire-retardant particles in a solution of a salt comprising the multivalent cation and a monovalent anion in a solvent; and obtaining the particles comprising the cores of fire-retardant particles and the shells of the inorganic salt comprising the multivalent cation and the multivalent anion encapsulating the cores.
  • the present disclosure provides the process of the twenty-first embodiment, wherein the aqueous solution further comprises a dispersant.
  • the present disclosure provides the process of the twenty-first or twenty-second embodiment, wherein the aqueous solution further comprises a monovalent anion.
  • the present disclosure provides the process of the twenty-second embodiment, wherein the monovalent anion is bicarbonate, hydrogen sulfate, or dihydrogen phosphate.
  • the mixture was blended for 3 minutes using a very high shear rotary blender, Model IKA T50 Ultra Turrax (IKA, Wilmington, NC). The blended mixture was allowed to sit for 15 minutes at 20 °C. The mixture was then centrifugated at 4,000 rpm using a centrifuge, Model EPPENDORF 5810 R (Eppendorf North America, Enfield, CT). The supernatant was discarded and the sedimented part was transferred to 300 g 10% aqueous solution of calcium chloride. The mixture was then blended for about 3 minutes using the rotary blender. The blended dispersion was left to sit for about 15 minutes at 20 °C. This blended dispersion was then centrifugated at 4,000 rpm. The supernatant was then discarded.
  • a very high shear rotary blender Model IKA T50 Ultra Turrax (IKA, Wilmington, NC).
  • the blended mixture was allowed to sit for 15 minutes at 20 °C.
  • the mixture was then centrifugated at 4,000 rpm using a centrifuge, Model
  • Example 2 The sedimented part was then resuspended in distilled water, shaken for 15 minutes using a Gyratory Shaker (New Brunswick Scientific Co., Enfield, CT) then and filtered using #1 Whatman Filter Paper). The resulting solids were then air dried and then vacuum dried in a vacuum oven at 40 °C for 60 minutes. Secondary electron imaging (SEI), SEM images were obtained using a JEOL 700 IF Field Emission Scanning Electron Microscope (JEOL USA, Inc., Peabody, MA). A comparison of the SEM images of uncoated and Example 1 particles indicated that the Example 1 particles had been encapsulated.
  • Example 2 Secondary electron imaging
  • Example 2 was prepared as described in Example 1 with the modification that “EXOLIT OP 935” was used instead of jet-milled, 5-micrometer TPPO.
  • Example 2 Particles 25 phr, 4.6 g
  • water 25 phr, 4.6 g
  • SUPER ESTER E-730-55 10 phr, 1.8 g
  • PROCETYL AWS-LQ-(AP)
  • Bum Test samples were constructed by coating adhesive onto 0.5 mil clear and 0.5 mil metallized polyethylene terephthalate (PET) using a Mayer Rod 14.
  • PET polyethylene terephthalate
  • the clear PET was corona treated, and the metallized PET was metallized with a layer of aluminum.
  • the samples were then dried in an oven set to 140 °F (60 °C) for 3 minutes.
  • a layer of scrim was then placed onto one side and the two adhesive layers were bound together to form a 6 in. (15.24 cm) wide by 21 in. (53.3 cm) sample construction comprising of clear PET, adhesive, scrim, adhesive, metalized PET.
  • a modified UL 181 Bum Test was then conducted on the PET sample constructions.
  • a Bum Test sample constmction was bonded to fiberglass, metal side out, and attached to a rod at a 45° angle.
  • a Bunsen burner flame was pre-set with a 2 in. to 2.5 in. (5.1 cm to 6.4 cm) soft yellow flame and placed just below the metallized PET.
  • a sample constmction passed the Bum Test where the flame selfextinguished before reaching an edge of the constmction.
  • a sample constmction failed the Bum Test where the sample constmction was burned to its edges.
  • a good pass is defined as burning less than 25% of the constmction and not burning to the edges of a sheet.
  • a pass bum is defined as burning less than 50% of the constmction and not burning to the edges of a sheet.
  • a slight pass bum is defined as burning less than 75% of the constmction and not burning to the edges of a sheet.
  • a slight fail is defined as burning greater than 50% of the constmction and not burning to the edges of a sheet.
  • a fail is defined as burning greater than 75% of the constmction and not burning to the edges of a sheet.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Les particules comprennent des noyaux de particules ignifuges et des enveloppes d'un sel inorganique encapsulant les noyaux. Le sel inorganique comprend un cation multivalent et un anion multivalent. L'invention concerne également des compositions et des articles comprenant les particules et des procédés de fabrication des particules et des compositions.
PCT/IB2021/061242 2020-12-04 2021-12-02 Agent ignifuge encapsulé et compositions et procédés associés WO2022118246A1 (fr)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE24906E (en) 1955-11-18 1960-12-13 Pressure-sensitive adhesive sheet material
US4138356A (en) 1973-08-22 1979-02-06 Champion International Corporation Encapsulated flame retardant system
US4329384A (en) 1980-02-14 1982-05-11 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape produced from photoactive mixture of acrylic monomers and polynuclear-chromophore-substituted halomethyl-2-triazine
US4330590A (en) 1980-02-14 1982-05-18 Minnesota Mining And Manufacturing Company Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-2-triazine
US4379201A (en) 1981-03-30 1983-04-05 Minnesota Mining And Manufacturing Company Multiacrylate cross-linking agents in pressure-sensitive photoadhesives
US4737559A (en) 1986-05-19 1988-04-12 Minnesota Mining And Manufacturing Co. Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers
US5073611A (en) 1989-04-29 1991-12-17 Basf Aktiengesellschaft Copolymers crosslinkable by ultraviolet radiation in the atmosphere
US20040126574A1 (en) * 2002-12-31 2004-07-01 Teraoka Seisakusho Co., Ltd. Flame retardant pressure-sensitive adhesive tape
US20090088495A1 (en) * 2007-10-02 2009-04-02 Fuji Xerox Co., Ltd. Flame-retardant particle, resin composition and resin formed body
US20100285313A1 (en) 2009-05-11 2010-11-11 Eternal Chemical Co., Ltd. Microencapsulated fire retardants and the uses thereof
US8309240B1 (en) 2009-02-28 2012-11-13 Hrl Laboratories, Llc Encapsulated fire-retardant materials to improve battery safety
US9102774B2 (en) 2010-12-21 2015-08-11 3M Innovative Properties Company Polymers derived from secondary alkyl (meth)acrylates
CN109880568A (zh) * 2019-03-04 2019-06-14 闽江学院 阻燃压敏胶及其应用

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE24906E (en) 1955-11-18 1960-12-13 Pressure-sensitive adhesive sheet material
US4138356A (en) 1973-08-22 1979-02-06 Champion International Corporation Encapsulated flame retardant system
US4329384A (en) 1980-02-14 1982-05-11 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape produced from photoactive mixture of acrylic monomers and polynuclear-chromophore-substituted halomethyl-2-triazine
US4330590A (en) 1980-02-14 1982-05-18 Minnesota Mining And Manufacturing Company Photoactive mixture of acrylic monomers and chromophore-substituted halomethyl-2-triazine
US4379201A (en) 1981-03-30 1983-04-05 Minnesota Mining And Manufacturing Company Multiacrylate cross-linking agents in pressure-sensitive photoadhesives
US4737559A (en) 1986-05-19 1988-04-12 Minnesota Mining And Manufacturing Co. Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers
US5073611A (en) 1989-04-29 1991-12-17 Basf Aktiengesellschaft Copolymers crosslinkable by ultraviolet radiation in the atmosphere
US20040126574A1 (en) * 2002-12-31 2004-07-01 Teraoka Seisakusho Co., Ltd. Flame retardant pressure-sensitive adhesive tape
US20090088495A1 (en) * 2007-10-02 2009-04-02 Fuji Xerox Co., Ltd. Flame-retardant particle, resin composition and resin formed body
US8309240B1 (en) 2009-02-28 2012-11-13 Hrl Laboratories, Llc Encapsulated fire-retardant materials to improve battery safety
US20100285313A1 (en) 2009-05-11 2010-11-11 Eternal Chemical Co., Ltd. Microencapsulated fire retardants and the uses thereof
US9102774B2 (en) 2010-12-21 2015-08-11 3M Innovative Properties Company Polymers derived from secondary alkyl (meth)acrylates
CN109880568A (zh) * 2019-03-04 2019-06-14 闽江学院 阻燃压敏胶及其应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Handbook of Pressure Sensitive Adhesive Technology", 1989
ALPHONSUS V. POCIUS: "Adhesion and Adhesives Technology", 1997, HANSER/GARDNER PUBLICATIONS, INC., pages: 216 - 223

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