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WO2015051364A1 - Superparticules comprenant des particules polymères creuses - Google Patents

Superparticules comprenant des particules polymères creuses Download PDF

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Publication number
WO2015051364A1
WO2015051364A1 PCT/US2014/059291 US2014059291W WO2015051364A1 WO 2015051364 A1 WO2015051364 A1 WO 2015051364A1 US 2014059291 W US2014059291 W US 2014059291W WO 2015051364 A1 WO2015051364 A1 WO 2015051364A1
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weight
supraparticles
supraparticle
μπι
hollow polymeric
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Nick G. Triantafillopoulos
I. John Westerman
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Omnova Solutions Inc
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Omnova Solutions Inc
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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
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene

Definitions

  • Embodiments of the invention are directed toward supraparticles including hollow polymeric particles.
  • Hollow polymeric particles are known. These particles generally include spheres of thermoplastic resin, such as polystyrene, that are formed by polymerizing the thermoplastic resin on an acid or ester-containing core. Removal of the core provides the thermoplastic sphere.
  • thermoplastic resin such as polystyrene
  • Embodiments of the invention are directed toward a method for forming a supraparticle, the method comprising combining a plurality of hollow polymeric particles with a binder polymer to form a blend; and spray drying the blend to produce a supraparticle.
  • a supraparticle comprising a core including a plurality of hollow polymeric particles and a binder layer surrounding the core.
  • Fig. 1 is a scanning electron micrograph (SEM) image of a supraparticle that has been severed to reveal its interior.
  • Fig. 2 is an SEM image of a plurality of supraparticles.
  • Fig. 3 is an SEM image of a supraparticle that has been severed to reveal its interior.
  • Fig. 4 is an SEM image of the core of a supraparticles that includes Ti02 particles.
  • Fig. 5 is a severed cross-sectional SEM image of supraparticle that includes Ti02 particles.
  • Embodiments of the invention are based, at least in part, on the discovery of supraparticles including hollow polymeric particles.
  • these supraparticles include a core of individual hollow polymeric particles enclosed in an outer shell or layer including binder. It has unexpectedly been discovered that these supraparticles self-assemble upon spray drying a blend of binder latex and hollow polymeric particles. It has also unexpectedly been discovered that these supraparticles are dispersible in water and yet remain appreciably intact. As a result, the resulting supraparticles demonstrate technologically useful porosity and are advantageously light weight.
  • these supraparticles can be prepared in the presence of organic and/or inorganic materials that, upon self-assembling of the supraparticles, encapsulate the organic and inorganic particles within the supraparticle. It is contemplated that these supraparticles can be used in personal care compositions, waste-water treatment and purification, and geotechnical applications.
  • Fig. 1 shows supraparticle 11 including a plurality of hollow polymeric particles 13 within a core 14 of supraparticle 11. Interstitial voids 15 exist between adjacent hollow polymeric particles 13 within core 14.
  • the individual hollow polymeric particles 13 are encapsulated or enclosed within a binder layer 17.
  • binder layer 17 surrounds core 14.
  • binder layer 17 includes binder polymer 18 and optionally hollow polymeric particles 13' located in binder layer 17.
  • an exterior layer of binder polymer 18 may form an outermost layer or skin 21 of binder layer 17.
  • binder polymer 18 includes coalesced polymer.
  • binder polymer 18 forms a matrix around hollow polymeric particles 13' within binder layer 17.
  • Fig. 2 shows that supraparticles 11 are generally spherical, although, as shown, the supraparticles can have other three-dimensional shapes such as supraparticles that are generally ovoidal in shape or generally torodial in shape.
  • the supraparticles of the present invention often take on a spherical shape, reference may be made throughout this specification to spherically-shaped supraparticles, although it should be understood that supraparticles 11 are not necessarily limited thereto unless specifically stated.
  • hollow polymeric particles 13 include internal voids 19.
  • Figs. 1 and 3 best show that binder polymer 18 is predominately, and in certain embodiments exclusively (to the extent appreciable), on the outer perimeter of supraparticles 11. Also, hollow polymeric particles 13 within core 14 of supraparticles 11 are not bound (i.e. they are loose) or appreciably not bound to one another. Instead, in one or more embodiments, hollow polymeric particles are encapsulated by binder layer 17. Stated another way, core 14 is appreciably free of binder polymer 18. In one or more embodiments, the amount, if any, of binder polymer 18 located within core 14 may be quantitatively described with respect to the total weight of binder polymer within supraparticle 11.
  • binder layer 17 includes that portion or region of supraparticle 11 where at least 70 wt%, in other embodiments 80 wt%, in other embodiments 90 wt%, in other embodiments 95 wt%, in other embodiments 98 wt%, and in other embodiments 99 wt% of binder polymer resides within supraparticle 11.
  • supraparticles 11 may include organic and/or inorganic materials besides the hollow polymeric particles and the binder.
  • organic and/or inorganic materials such as those in the form of particles, may be distributed throughout the supraparticles.
  • inorganic particles 25 are located in interstitial voids 15 of supraparticles 11.
  • inorganic particles 25 are generally distributed randomly, or in other embodiments statistically, throughout supraparticle 11.
  • the size of the supraparticles which includes a distribution of sizes, can be described with respect to the particles sizes within a percentile of the whole population of a given sample.
  • the particle sizes can be described with respect to the 90 th percentile (i.e. d90), 50 th percentile (i.e. d50), and 10 th percentile (i.e. dlO) of a given population.
  • 90 th percentile i.e. d90
  • 50 th percentile i.e. d50
  • 10 th percentile i.e. dlO
  • one useful technique employed in measuring the particles described herein is the use of a laser defractor-based particles size analyzer, which ultimately provides spherical diameters for the particles measured.
  • the supraparticles may have a d90 diameter (i.e. 90 % of the particles have a diameter) of at least 5 ⁇ , in other embodiments at least 10 ⁇ , and in other embodiments at least 15 ⁇ . In these or other embodiments, the supraparticles may have d90 diameter of at most 120 ⁇ , in other embodiments at most 100 ⁇ , and in other embodiments at most 80 ⁇ . In one or more embodiments, the supraparticles may have d90 diameter of from about 5 to about 120 ⁇ , in other embodiments from about 10 to about 100 ⁇ , and in other embodiments from about 15 to about 80 ⁇ .
  • the supraparticles may have a d50 diameter (i.e. 50 % of the particles have a diameter) of at least 5 ⁇ , in other embodiments at least 10 ⁇ , and in other embodiments at least 15 ⁇ . In these or other embodiments, the supraparticles may have d50 diameter of at most 80 ⁇ , in other embodiments at most 70 ⁇ , and in other embodiments at most 60 ⁇ . In one or more embodiments, the supraparticles may have d50 diameter of from about 5 to about 80 ⁇ , in other embodiments from about 10 to about 70 ⁇ , and in other embodiments from about 15 to about 60 ⁇ .
  • the supraparticles may have a dlO diameter (i.e. 10 % of the particles have a diameter) of at least 5 ⁇ , in other embodiments at least 10 ⁇ , and in other embodiments at least 15 ⁇ . In these or other embodiments, the supraparticles may have dlO diameter of at most 60 ⁇ , in other embodiments at most 50 ⁇ , and in other embodiments at most 40 ⁇ . In one or more embodiments, the supraparticles may have dlO diameter of from about 5 to about 60 ⁇ , in other embodiments from about 10 to about 50 ⁇ , and in other embodiments from about 15 to about 40 ⁇ .
  • binder layer 17 may have thickness of at least 5 nm, in other embodiments at least 50 nm, and in other embodiments at least 100 nm. In these or other embodiments, the thickness of binder layer 17 may be at most 7 ⁇ , in other embodiments at most 5 ⁇ , in other embodiments at most 3 ⁇ , in other embodiments at most 2 ⁇ , in other embodiments at most 1 ⁇ , and in other embodiments at most 0.5 ⁇ .
  • the thickness of the exterior binder layer may be from about 5 nm to about 2 ⁇ , in other embodiments from about 5 nm to about 7 ⁇ , in other embodiments from about 50 nm to about 5 ⁇ , in other embodiments from about 50 nm to about 3 ⁇ , in other embodiments from about 50 nm to about 1 ⁇ , and in other embodiments from about 100 nm to about 0.5 ⁇ .
  • the individual hollow polymeric particles are hollow spheres formed from a thermoplastic resin.
  • the hollow polymeric particles include a porous outer shell, which may include a sphere wherein surface pores traverse the outer surface of the sphere and connect to the interior hollow void of the hollow polymeric particles.
  • the thermoplastic resin of the shell has a glass transition temperature (Tg) of at least 80 °C, in other embodiments at least 90 °C, and in other embodiments at least 100 °C.
  • the hollow spheres which may also be referred to as polymeric shells, may include, in polymerized form, at least one of styrene; methyl methacrylate; methacrylic acid; acrylic acid, allyl methacrylate, divinyl benzene; and combinations of two or more thereof.
  • the hollow sphere includes polystyrene or copolymers of styrene and comonomer.
  • the hollow sphere may include, based on 100 parts by weight of the total monomers used to form the shell, from about 75 to about 100 parts styrene; from about 0 to about 25 parts methyl methacrylate; from about 0 to about 3 parts methacrylic acid; from about 0 to about 3 parts acrylic acid; and from about 0 to about 5 parts allyl methacrylate and/ or divinyl benzene.
  • the size of the individual hollow polymeric particles within the supraparticles may have an average particle size (i.e. particle diameter) of at least 0.5 ⁇ , in other embodiments at least 0.7 ⁇ , and in other embodiments at least 0.9 ⁇ .
  • the individual hollow polymeric particles may have an average particle size of at most 1.5 ⁇ , in other embodiments at most 1.3 ⁇ , and in other embodiments at most 1.1 ⁇ .
  • the individual hollow polymeric particles may have an average particle size of from about 0.5 to about 1.5 ⁇ , in other embodiments from about 0.7 to about 1.3 ⁇ , and in other embodiments from about 0.9 to about 1.1 ⁇ .
  • the internal void volume of the individual hollow spheres within the supraparticles may be at least 45 %, in other embodiments at least 55 %, and in other embodiments at least 65 % of the total volume of the hollow spheres. In these or other embodiments, the internal void volume may be at most 95 %, in other embodiments at most 85 %, and in other embodiments at most 75 % of the total volume of the hollow spheres. In one or more embodiments, the internal void volume may be from about 45 to about 95 %, in other embodiments from about 55 to about 85 %, and in other embodiments from about 55 to about 75 % of the total volume of the hollow spheres.
  • the hollow polymeric particles can include, but are not limited to, those produced through an acid core process and/or those produced through an ester core process.
  • hollow polymeric particles produced using an acid core process can be found in U.S. Pat. No. 4,468,498 to Kowalski, which is incorporated herein by reference in its entirety.
  • hollow polymeric particles produced using an ester core process can be found in U.S. Pat. Nos. 5,157,084 to Lee, 5,521,253 to Lee, and US Pat. Pub. 2010/0317753 all of which are incorporated herein by reference in their entirety.
  • the creation of pores in the porous outer shell may be inherent in the production of the hollow polymeric pigments.
  • the porosity of the outer shell may be increased by including a hydrolysable monomer in the shell formation stage of the production of the hollow polymeric pigment.
  • An example of hollow polymeric pigments produced with the inclusion of hydrolyzable monomers in the shell formation can be seen in WO 2010/120344 which is incorporated herein by reference.
  • useful binder resins include film-forming binder resins.
  • film-forming binder resins coalesce to form a film.
  • the film-forming binder resins are characterized by a minimum film formation temperature (MFFT), which is the minimum temperature required to coalesce the binder when laid on a substrate as a film, of less than 100 °C, in other embodiments less than 90 °C, and in other embodiments less than 80 °C.
  • MFFT minimum film formation temperature
  • the film-forming binder has a minimum film formation temperature from about 50 °C to about 100 °C, and in other embodiments from about 60 °C to about 90 °C, and in other embodiments from about 70°C to about 80 °C.
  • MFFT may be determined according to ASTM D2354.
  • useful film-forming binders may be characterized by a glass transition temperature (Tg) of at least 40 °C, in other embodiments at least 50 °C, and in other embodiments at least 60 °C.
  • Tg of the film-forming binder may be at most 90 °C, in other embodiments at most 80 °C, and in other embodiments at most 70 °C.
  • the Tg of the film-forming binder may be from about 40 °C to about 90 °C, in other embodiments from about 50 °C to about 80 °C, and in other embodiments from about 60 °C to about 80 °C.
  • the glass transition temperature of the film- forming binder may be described relative to the glass transition temperature of the hollow polymeric particle. In one or more embodiments, the glass transition temperature of the film-forming resin is at least 15 °C, in other embodiments at least 10 °C, in and in other embodiments at least 5 °C lower than the glass transition temperature of the hollow polymeric sphere.
  • the film-forming binder may be characterized by a gel content of at of at least 40 %, in other embodiments at least 50 %, and in other embodiments at least 60 %. In these or other embodiments, the gel content of the film- forming binder may be at most 90 %, in other embodiments at most 80 %, and in other embodiments at most 70 %. In one or more embodiments, the gel content of the film- forming binder may be from about 40 to about 90 %, in other embodiments from about 50 % to about 80 %, and in other embodiments from about 60 % to about 80 %.
  • the film-forming binder may include copolymers that derive from copolymerization of alkenyl aromatic monomer together with one or more of aliphatic conjugated diene monomer, ethylenically unsaturated nitrile monomer, ethylenically unsaturated acid monomer, ethylenically unsaturated functional monomer, ethylenically unsaturated non-functional ester monomer, and other monomer copolymerizable therewith.
  • the film-forming binder includes a copolymer including (in polymerized form) alkenyl aromatic monomer, aliphatic conjugated diene monomer, ethyleneically unsaturated nitrile monomer, and at least one functional monomer.
  • the film-forming binder is a latex polymer, and therefore reference may be made to polymeric particles.
  • alkenyl aromatic monomer examples include styrene, alpha-methyl styrene, p-tertiary butyl styrene, methyl vinyl toluene, p-vinyl toluene, divinyl benzene, and 3-ethyl styrene, or mixtures thereof.
  • diene monomers examples include piperylene, isoprene, 2,3-dimethyl-l,3- butadiene, l,3-cyclohexadiene,l,3-butadiene, or mixtures thereof.
  • nitriles of ethylenically unsaturated carboxylic acid examples include acrylonitrile and methacrylonitrile.
  • acrylonitrile is the most popular nitrile of ethylenically unsaturated carboxylic acids, reference may be simply made to acrylonitrile, but unless otherwise specified, is not intended to limit beyond nitriles of ethylenically unsaturated carboxylic acid.
  • acid-bearing monomers examples include ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, fumaric acid, crotonic acid, maleic acid, itaconic acid, 2-carboxyethylacrylate, 2-acrylamido-2-methylbutanoic acid, and the like, and combinations of two or more such acids.
  • carboxylic acid monomers such as acrylic acid, methacrylic acid, fumaric acid, crotonic acid, maleic acid, itaconic acid, 2-carboxyethylacrylate, 2-acrylamido-2-methylbutanoic acid, and the like, and combinations of two or more such acids.
  • functional monomer includes monomer that will provide electronic stabilization to the particles in latex.
  • functional monomers include hydroxyl and/or amide functionality or groups.
  • the simple presence of a carboxyl group, such as may be present in an ester group or moiety, is not considered a functional group.
  • functional monomer may include various organic salts, for example sodium styrene sulfonate, sodium methallyl sulfonate, the alkali, ammonium, and amine salts of 2-acrylamido-2-methylpropanesulfonate, and the 3- sulfopropyl(meth)acrylate salt of sodium or potassium.
  • AMPS AMPS
  • Na-AMPS reference can be made to U.S. Pat. No. 6,184,287, which is incorporated herein by reference.
  • Examples of amides of ethylenically unsaturated carboxylic acid include various unsaturated amides or derivatives thereof having a total of from about 3 to about 12 carbon atoms.
  • Examples of unsaturated amides or derivatives thereof include acrylamide, methacrylamide, N,N-methylenebisacrylamide, N-methylolacrylamide, N- methylolmethacrylamide, N-ethyoxymethylacrylamide, N-butoxymethylacrylamide, N- isobutoxymethylacrylamide, N,N-dimethylacrylamide, derivatives thereof, and mixtures thereof.
  • hydroxyl-containing monomers include hydroxyl derivatives of acrylates and methacrylates.
  • the alkyl portion of these compounds includes from 1 to 10, optionally from 1 to 4, carbon atoms.
  • ester derivatives include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and ethylene oxide extended derivatives of ethyleneglycol methacrylate.
  • non-functional esters of ethylenically unsaturated carboxylic acid include alkyl (meth) acrylates. These monomers are devoid of acid, hydroxyl, and amide groups. Examples include methylacrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, iso-decylacrylate, propyl acrylate, ethyl acrylate, ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, diethyleneglycol diacrylate, diethyleneglycol dimethacrylate, triethyleneglycol diacrylate, and triethyleneglycol dimethacrylate.
  • alkyl (meth) acrylates These monomers are devoid of acid, hydroxyl, and amide groups. Examples include methylacrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, iso-decylacrylate, propyl acrylate, e
  • the film-forming binder includes copolymers that include (in polymerized form) at least 45 weight %, in other embodiments at least 50 weight %, in other embodiments at least 55 weight %, and in other embodiments at least 60 weight % mer units deriving from the polymerization of alkenyl aromatic (e.g. styrene), based on the total weight of the mer units within the particles.
  • copolymers that include (in polymerized form) at least 45 weight %, in other embodiments at least 50 weight %, in other embodiments at least 55 weight %, and in other embodiments at least 60 weight % mer units deriving from the polymerization of alkenyl aromatic (e.g. styrene), based on the total weight of the mer units within the particles.
  • the film-forming binder includes copolymers that include less than 95 weight %, in other embodiments less than 90 weight %, in other embodiments less than 85 weight %, and in other embodiments less than 80 weight % mer units deriving from the polymerization of alkenyl aromatic (e.g. styrene), based on the total weight of the mer units within the particles.
  • alkenyl aromatic e.g. styrene
  • the film-forming binder includes copolymers that include at least 10 weight %, in other embodiments at least 15 weight %, in other embodiments at least 20 weight %, and in other embodiments at least 25 weight % mer units deriving from the polymerization of conjugated diene monomer (e.g. 1,3- butadiene) based on the total weight of the mer units within the particles.
  • conjugated diene monomer e.g. 1,3- butadiene
  • the film-forming binder includes copolymers that include less than 50 weight %, in other embodiments less than 45 weight %, in other embodiments less than 40 weight %, and in other embodiments less than 35 weight % mer units deriving from the polymerization of conjugated diene (e.g. 1,3-butadiene), based on the total weight of the mer units within the particles.
  • conjugated diene e.g. 1,3-butadiene
  • the film-forming binder includes copolymers that include at least 5 weight %, in other embodiments at least 8 weight %, in other embodiments at least 10 weight %, and in other embodiments at least 12 weight % mer units deriving from the polymerization of acrylonitrile, based on the total weight of the mer units within the particles.
  • the film-forming binder includes copolymers that include less than 30 weight %, in other embodiments less than 25 weight %, in other embodiments less than 20 weight %, and in other embodiments less than 15 weight % mer units deriving from the polymerization of acrylonitrile, based on the total weight of the mer units within the particles.
  • the film-forming binder includes copolymers may include at least 0.2 weight %, in other embodiments at least 0.5 weight %, in other embodiments at least 1 weight %, and in other embodiments at least 2.0 weight % mer units deriving from the polymerization of acid monomer (e.g. itaconic acid), based on the total weight of the mer units within the particles.
  • the copolymers may include less than 8 weight %, in other embodiments less than 7 weight %, in other embodiments less than 5 weight %, and in other embodiments less than 3 weight % mer units deriving from the polymerization of acid monomer (e.g. itaconic acid), based on the total weight of the mer units within the particles.
  • the copolymers are devoid or substantially devoid of acid-bearing monomer.
  • the film-forming binder includes copolymers that may include at least 0.1 weight %, in other embodiments at least 0.2 weight %, in other embodiments at least 0.3 weight %, and in other embodiments at least 0.4 weight % mer units deriving from the polymerization of functional monomer (e.g. Na-AMPS), based on the total weight of the mer units within the particles.
  • the film-forming binder includes copolymers that include less than 3 weight %, in other embodiments less than 2 weight %, in other embodiments less than 1.5 weight %, and in other embodiments less than 1.0 weight % mer units deriving from the polymerization of functional monomer (e.g. Na-AMPS), based on the total weight of the mer units within the particles.
  • the copolymers are devoid or substantially devoid of functional monomer.
  • the film-forming binder includes copolymers that may include at least 0.2 weight %, in other embodiments at least 0.5 weight %, in other embodiments at least 0.8 weight %, and in other embodiments at least 1.2 weight % mer units deriving from the polymerization of amide monomer, based on the total weight of the mer units within the particles.
  • the copolymers may include less than 5 weight %, in other embodiments less than 4 weight %, in other embodiments less than 3 weight %, and in other embodiments less than 2 weight % mer units deriving from the polymerization of amide monomer, based on the total weight of the mer units within the particles.
  • the copolymers are devoid or substantially devoid of amide monomer.
  • the film-forming binder includes copolymer that may include at least 0.2 weight %, in other embodiments at least 0.5 weight %, in other embodiments at least 0.8 weight %, and in other embodiments at least 1.2 weight % mer units deriving from the polymerization of hydroxyl monomer, based on the total weight of the mer units within the particles.
  • the copolymers may include less than 5 weight %, in other embodiments less than 4 weight %, in other embodiments less than 3 weight %, and in other embodiments less than 2 weight % mer units deriving from the polymerization of hydroxyl monomer, based on the total weight of the mer units within the particles.
  • the copolymers are devoid or substantially devoid of hydroxyl monomer.
  • the film-forming binder includes copolymers that may include at least 0.2 weight %, in other embodiments at least 0.5 weight %, in other embodiments at least 1 weight %, and in other embodiments at least 2 weight % mer units deriving from the polymerization of non-functional ester monomer, based on the total weight of the mer units within the particles.
  • the copolymers may include less than 5 weight %, in other embodiments less than 3 weight %, in other embodiments less than 2 weight %, in other embodiments less than 1 weight %, in other embodiments less than 0.5 weight %, and in other embodiments less than 0.1 weight % mer units deriving from the polymerization of non-functional ester monomer, based on the total weight of the mer units within the particles.
  • the copolymers are devoid or substantially devoid of non-functional monomer.
  • useful inorganic particles include one or more mineral fillers or pigments.
  • the mineral fillers are heavy or highly dense mineral fillers.
  • the inorganic particles may include synthetic materials.
  • the inorganic particles may be characterized by an average particle size of less than 2 ⁇ , in other embodiments less than 1.0 ⁇ , and in other embodiments less than 0.7 ⁇ . In these or other embodiments, the inorganic particles may have an average particle size of from about 5 nm to about 2 ⁇ , in other embodiments from about 25 nm to about 1.0 ⁇ , and in other embodiments from about 50 nm to about 0.7 ⁇ .
  • the inorganic particles may include dense minerals such as barite, hematite, and magnesium oxide.
  • the inorganic particles may include titanium oxide, calcium oxide, zinc oxide, and magnesium oxide.
  • the inorganic particles include clays.
  • Useful clays include mineral clays, which may also be referred to as hydrous aluminum silicates. These clays include kaolin (i.e. kaolinite) clays and smectite clays. Examples of smectite clays include, montmorillonite, hectorite, nontrite, beidellite, volkonskoite, saponite, sauconite, sobockite, sterensite, and sinfordite clays.
  • the clays are layered clays, which may include a plurality of stacked platelets that may include or be modified to include cationically exchangeable ions between the platelets.
  • Exemplary smectite clays of this nature are known in the art as described in U.S. Patent Nos 5,552,469, 6,818,693, and 7,019,063, which are incorporated herein by reference.
  • the supraparticles may be prepared by combining hollow polymeric particles with a binder to form a blend, and then spray drying the blend to produce the supraparticles. During the spray drying process, the hollow polymeric particles self-assemble into the supraparticles. Accordingly, reference may be made to self-assembled particles or self-assembled supraparticles.
  • the blend is in the form of a latex wherein the solids portion of the latex includes the hollow polymeric particles and the binder.
  • the latex may also include optional inorganic particles, as well as other constituents that may facilitate formation of the blend or spray drying of the same.
  • Exemplary additional ingredients include partitioning agents. Exemplary portioning agents include various aliphatic waxes.
  • the blend which may also be referred to as the sprayable latex or emulsion, includes at least 10, in other embodiments at least 20, and in other embodiments at least 30 percent by weight solids based on the total weight of the latex.
  • the sprayable latex includes at most 70, in other embodiments at most 60, and in other embodiments at most 50 percent by weight solids based on the total weight of the latex.
  • the latex includes from about 10 to about 70, in other embodiments from about 20 to about 60, and in other embodiments from about 30 to about 50 percent by weight solids based on the total weight of the latex.
  • the solids portion of the sprayable latex includes at least 40, in other embodiments at least 50, and in other embodiments at least 60 percent by weight hollow polymeric particles based on the total weight of the solids. In these or other embodiments, the solids portion of the sprayable latex includes at most 90, in other embodiments at most 80, and in other embodiments at most 70 percent by weight hollow polymeric particles based on the total weight of the solids. In one or more embodiments, the solids portion of the latex includes from about 40 to about 90, in other embodiments from about 50 to about 80, and in other embodiments from about 60 to about 70 percent by weight hollow polymeric particles based on the total weight of the solids.
  • the solids portion of the sprayable latex includes at least 10, in other embodiments at least 15, and in other embodiments at least 20 percent by weight binder resin based on the total weight of the solids. In these or other embodiments, the solids portion of the sprayable latex includes at most 40, in other embodiments at most 30, and in other embodiments at most 25 percent by weight binder resin based on the total weight of the solids. In one or more embodiments, the solids portion of the latex includes from about 10 to about 40, in other embodiments from about 15 to about 30, and in other embodiments from about 20 to about 25 percent by weight binder resin based on the total weight of the solids.
  • the solids portion of the sprayable latex includes at least 10, in other embodiments at least 15, and in other embodiments at least 20 percent by weight inorganic particles based on the total weight of the solids. In these or other embodiments, the solids portion of the sprayable latex includes at most 40, in other embodiments at most 30, and in other embodiments at most 25 percent by weight inorganic particles based on the total weight of the solids. In one or more embodiments, the solids portion of the latex includes from about 10 to about 40, in other embodiments from about 15 to about 30, and in other embodiments from about 20 to about 25 percent by weight inorganic particles based on the total weight of the solids.
  • the solids portion of the sprayable latex includes at least 0.5, in other embodiments at least 1, and in other embodiments at least 2 percent by weight partitioning agent based on the total weight of the solids. In these or other embodiments, the solids portion of the sprayable latex includes at most 10, in other embodiments at most 8, and in other embodiments at most 5 percent by weight partitioning agent based on the total weight of the solids. In one or more embodiments, the solids portion of the latex includes from about 0.5 to about 10, in other embodiments from about 1 to about 8, and in other embodiments from about 2 to about 5 percent by weight partitioning agent based on the total weight of the solids.
  • the sprayable latex is spray dried using conventional atomization techniques.
  • Exemplary spray drying processes that may be used include those disclosed in U.S. Pat. No. 6,013,594, which is incorporated herein by reference. PHYSICAL PROPERTIES OF SUPRAPARTICLES
  • the supraparticles are, on a macro scale, dry powders.
  • the supraparticles are free-flowing powders.
  • the dry powder lacks the visible appearance of moisture.
  • dry powder contains a moisture content of less than about 5 wt %, in other embodiments less than 3 wt %, and in other embodiments less than 1 wt % water.
  • the supraparticles may be characterized by a specific surface area that is at least 2 m ⁇ /g, in other embodiments at least 3 m ⁇ /g, and in other embodiments at least 4 m2/g. In these or other embodiments, the supraparticles may be characterized by a specific surface area that is at most 10 m2/g, in other embodiments at most 8 m ⁇ /g, and in other embodiments at most 7 m ⁇ /g- In certain embodiments the supraparticles may be characterized by a specific surface area that is from about 2 to about 10 m2/g, in other embodiments from about 3 to about 8 m ⁇ /g, and in other embodiments from about 4 to about 7 m ⁇ /g- specific surface area can be determined by using a BET surfanalyzer.
  • the supraparticles may be characterized by a bulk density that is at least 0.05 g/cc, in other embodiments at least 0.15 g/cc, and in other embodiments at least 0.20 g/cc. In these or other embodiments, the supraparticles may be characterized by a bulk density that is at most 0.50 g/cc, in other embodiments at most 0.40 g/cc, and in other embodiments at most 0.30 g/cc.
  • the supraparticles may be characterized by a bulk density that is from about 0.05 g/cc to about 0.50 g/cc, in other embodiments from about 0.15 g/cc to about 0.40 g/cc, and in other embodiments from about 0.20 g/cc to about 0.30 g/cc.
  • the supraparticles may be characterized by an apparent density that is at least 0.07, in other embodiments at least 0.15, and in other embodiments at least 0.25 g/cc. In these or other embodiments, the supraparticles may be characterized by an apparent density that is at most 1.0, in other embodiments at most 0.8, and in other embodiments at most 0.7 g/cc. In certain embodiments the supraparticles may be characterized by an apparent density that is from about 0.07 to about 1.0 g/cc, in other embodiments from about 0.15 to about 0.8 g/cc, and in other embodiments from about 0.25 to about 0.7 g/cc.
  • the supraparticles may be characterized by a total pore area that is at least 50 m ⁇ /g, in other embodiments at least 70 m ⁇ /g, and in other embodiments at least 90 m2/g.
  • Total pore area can be determined by using mercury porosimetry.
  • the supraparticles may be characterized by a pore median diameter that is at least 0.03 ⁇ , ⁇ , in other embodiments at least 0.05 ⁇ , and in other embodiments at least 0.15 /xm. In these or other embodiments, the supraparticles may be characterized by a pore median diameter that is at most 0.2 /xm, in other embodiments at most 0.15 ⁇ , and in other embodiments at most 0.10 ⁇ . In certain embodiments, the supraparticles may be characterized by a pore median diameter that is from about 0.03 ⁇ to about 0.2 ⁇ , in other embodiments from about 0.05 ⁇ to about 0.15 ⁇ , and in other embodiments from about 0.07 ⁇ to about 0.10 ⁇ . Total pore median diameter can be determined using mercury porosimetry
  • the supraparticles may be characterized by a percent porosity that is at least 20 %, in other embodiments at least 25 %, and in other embodiments at least 30 %. In these or other embodiments, the supraparticles may be characterized by a percent porosity that is at most 60 %, in other embodiments at most 55 %, and in other embodiments at most 50 %. In certain embodiments, the supraparticles may be characterized by a percent porosity that is from about 20 to about 60 %, in other embodiments from about 25 to about 55 %, and in other embodiments from about 30 to about 50 %.
  • the supraparticles may be characterized by a jojoba oil absorption that is at least 100, in other embodiments at least 120, and in other embodiments at least 130 grams oil per 100 grams of powder.
  • the supraparticles may be characterized by a jojoba oil absorption that is at most 300, in other embodiments at most 250, and in other embodiments at most 200 grams oil per 100 grams of powder.
  • the supraparticles may be characterized by a jojoba oil absorption that is from about 100 to about 300, in other embodiments from about 120 to about 250, and in other embodiments from about 130 to about 200 grams oil per 100 grams of powder.
  • the supraparticles of this invention may be used in personal care compositions.
  • the supraparticles can be used as base materials in cosmetics. It has been advantageously discovered that the supraparticles of the present invention have high oil absorbency, softness, and refract light, which makes them very advantageous for use in cosmetics.
  • the supraparticles can be used in sunscreens. It has advantageously been discovered that the supraparticles of the present invention can serve as carriers for reflective pigments such as titianium oxide and zinc oxide, wherein the pigments are well dispersed, which makes them very advantageous for use as sunscreens.
  • the supraparticles may be used as proppants in geotechnical applications such as hydraulic fracturing (i.e. "fracking"). It has advantageously been discovered that the supraparticles of the present invention exhibit high strength and crush resistance when dispersed in fluids, which makes them very advantageous for use as proppants.
  • the supraparticles may be used in drilling fluids such as drilling muds, drilling cements, and fracking fluids for oil and gas drilling operations. It has advantageously been discovered that the supraparticles of the present invention are light weight and exhibit high buoyancy, which makes them very advantageous for use in drilling fluids, such as carriers for heavy materials.
  • the supraparticles can be used in water purification including the treatment of wastewater and in the purification of drinking water. It has advantageously been discovered that the supraparticles of the present invention are highly absorbent, which makes them very advantageous for use as filter media.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Superparticules comprenant un assemblage de particules polymères creuses encapsulées par une couche de liant polymère.
PCT/US2014/059291 2013-10-05 2014-10-06 Superparticules comprenant des particules polymères creuses Ceased WO2015051364A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2019056062A1 (fr) * 2017-09-20 2019-03-28 The Bionics Institute Of Australia Superparticules améliorées
RU2777893C2 (ru) * 2018-06-27 2022-08-11 Кимберли-Кларк Ворлдвайд, Инк. Нанопористые сверхвпитывающие частицы
US11596924B2 (en) 2018-06-27 2023-03-07 Kimberly-Clark Worldwide, Inc. Nanoporous superabsorbent particles
US12076447B2 (en) 2017-07-28 2024-09-03 Kimberly-Clark Worldwide, Inc. Absorbent article containing nanoporous superabsorbent particles
US12194435B2 (en) 2017-07-28 2025-01-14 Kimberly-Clark Worldwide, Inc. Nanoporous superabsorbent particles

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US3371053A (en) * 1965-08-09 1968-02-27 Raskin Betty Lou Multicellular plastic particles and dispersions thereof
WO1995025129A1 (fr) * 1994-03-17 1995-09-21 Exxon Chemical Patents Inc. Polymere seche par pulverisation pour support de catalyseur
WO1997048732A2 (fr) * 1996-06-21 1997-12-24 Cytec Technology Corp. Compositions polymeres seches par pulverisation et procedes d'utilisation
WO2001000712A1 (fr) * 1999-06-24 2001-01-04 Dynea Chemicals Oy Granule pigmentaire sec et son procede de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3371053A (en) * 1965-08-09 1968-02-27 Raskin Betty Lou Multicellular plastic particles and dispersions thereof
WO1995025129A1 (fr) * 1994-03-17 1995-09-21 Exxon Chemical Patents Inc. Polymere seche par pulverisation pour support de catalyseur
WO1997048732A2 (fr) * 1996-06-21 1997-12-24 Cytec Technology Corp. Compositions polymeres seches par pulverisation et procedes d'utilisation
WO2001000712A1 (fr) * 1999-06-24 2001-01-04 Dynea Chemicals Oy Granule pigmentaire sec et son procede de fabrication

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12076447B2 (en) 2017-07-28 2024-09-03 Kimberly-Clark Worldwide, Inc. Absorbent article containing nanoporous superabsorbent particles
US12194435B2 (en) 2017-07-28 2025-01-14 Kimberly-Clark Worldwide, Inc. Nanoporous superabsorbent particles
WO2019056062A1 (fr) * 2017-09-20 2019-03-28 The Bionics Institute Of Australia Superparticules améliorées
US11369661B2 (en) 2017-09-20 2022-06-28 The Bionics Institute Of Australia Method of treatment
US12048733B2 (en) 2017-09-20 2024-07-30 The Bionics Institute Of Australia Method of treatment
RU2777893C2 (ru) * 2018-06-27 2022-08-11 Кимберли-Кларк Ворлдвайд, Инк. Нанопористые сверхвпитывающие частицы
US11596924B2 (en) 2018-06-27 2023-03-07 Kimberly-Clark Worldwide, Inc. Nanoporous superabsorbent particles

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