WO2012000184A1 - Inorganic nanoporous particles with water dispersible polyurethane binder - Google Patents

Inorganic nanoporous particles with water dispersible polyurethane binder Download PDF

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Publication number
WO2012000184A1
WO2012000184A1 PCT/CN2010/074811 CN2010074811W WO2012000184A1 WO 2012000184 A1 WO2012000184 A1 WO 2012000184A1 CN 2010074811 W CN2010074811 W CN 2010074811W WO 2012000184 A1 WO2012000184 A1 WO 2012000184A1
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WO
WIPO (PCT)
Prior art keywords
article
particles
water dispersible
dispersible polyurethane
inorganic nanoporous
Prior art date
Application number
PCT/CN2010/074811
Other languages
French (fr)
Inventor
Yahong Zhang
Yanli Huo
Stéphane Costeux
Thomas H Kalantar
Original Assignee
Dow Global Technologies Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Llc filed Critical Dow Global Technologies Llc
Priority to CA2801139A priority Critical patent/CA2801139A1/en
Priority to ES10853889.3T priority patent/ES2549166T3/en
Priority to PCT/CN2010/074811 priority patent/WO2012000184A1/en
Priority to EP10853889.3A priority patent/EP2588517B1/en
Priority to RU2013103804/05A priority patent/RU2543216C2/en
Priority to US13/698,185 priority patent/US20130091682A1/en
Priority to JP2013516951A priority patent/JP5571851B2/en
Priority to CN201080067861.1A priority patent/CN102985470B/en
Publication of WO2012000184A1 publication Critical patent/WO2012000184A1/en

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78—Heat insulating elements
    • E04B1/80—Heat insulating elements slab-shaped
    • E04B1/806—Heat insulating elements slab-shaped with air or gas pockets included in the slab
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/778—Nanostructure within specified host or matrix material, e.g. nanocomposite films
    • Y10S977/781—Possessing nonosized surface openings that extend partially into or completely through the host material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49826—Assembling or joining

Definitions

  • the present invention relates to an article of manufacture, a process for
  • the article of manufacture comprises inorganic nanoporous particles bound together with a water dispersible polyurethane binder.
  • Inorganic nanoporous materials such as aerogel materials offer tremendous thermal insulation properties.
  • aerogel materials are not currently useful in building and construction applications due to cost and delicate mechanical properties.
  • Preparing aerogel materials in a construction-sized solitary plank is currently not feasible, certainly not in the cost range of traditional insulating foam boards and planks.
  • Part of the process for producing aerogels requires removing a large volume of solvent from the nanopore structure, typically by extraction with supercritical carbon dioxide in an autoclave or by other demanding drying methods.
  • Such a process is daunting for a construction-sized solitary plank.
  • aerogels tend to be friable and crumble to powder readily under abrasive force, which is common during handling on a construction site. Therefore, it is desirable to develop a plank of aerogel-like material that is less costly than casting a solitary aerogel plank and that is less friable than a solitary aerogel plank.
  • compositions that combine a polymeric foam matrix comprising an aerogel component comprising an aerogel component.
  • US2008/0287561 describes polymeric foams containing aerogel particles dispersed in the polymer matrix. The aerogel particles require a coating to prevent polymer from penetrating pores of the aerogel material.
  • US 6,136,216 describes a composition of aerogel and gelatin that is foamed. The composition is shapcable into various shapes.
  • US 5,137,927 describes a polystyrene foam containing aerogel particles dispersed therein.
  • WO2007/146945 A2 describes flexible open cell foam/aerogel composites. In each of these references a foam binder contains aerogel particles.
  • US2010/0080949 describes using polymer/silica hybrid aerogel particles or beads covalently bonded with a binder to prepare aerogel composites.
  • the aerogel particles of this invention are a hybrid of inorganic and organic materials.
  • US 5,656,195 describes aerogel moldings that require 0.5 to 10 weight-percent sheet silicates and/or clay minerals based on aerogel weight to improve breaking strength.
  • US2004/0077738 describes a layered insulation article that includes a component comprising aerogel, and aqueous binder and hollow non- porous particles presumably to reduce the density of the article.
  • Flexibility is desirable in an aerogel structure in addition to low density and thermal insulation properties, particularly for building and construction insulation applications where the insulating material may need to conform to various shapes in shipping, handling and application.
  • the United States National Aeronautics and Space Administration has reported on recent developments on flexible crosslinked aerogel monolithic articles that comprise a polymerized and chemically bound coating over the aerogel structure (see publication LEW-18265-1 dated 04-06-09). Some degree of flexibility is also evident in articles of amine-modified aerogel monoliths crosslinked with di-isocyanate molecules (see, Capadona, et al., Polymer 47 (2006) 5754-5761). Both of these processes require casting a single aerogel monolithic crosslinked structure, a process that is a daunting task for construction-sized insulating articles.
  • a thermally insulating structure particularly a flexible thermally insulating structure, comprising mostly inorganic nanoporous particles such as aerogel particles bonded together with a binder, but without a functional coating on the inorganic nanoporous particles is desirable. Still more desirable is such a structure that does not require a coating on the inorganic nanoporous particles, the presence of hollow non-porous particles or the presence of sheet silicates or clay minerals to achieve low density, flexibility and strength.
  • the present invention provides a solution to this objective by forming an article of inorganic nanoporous particles using water dispersible polyurethane as a binder for inorganic nanoporous particles.
  • the present invention is an article comprising inorganic nanoporous particles bound together by water dispersible polyurethane, the article comprising 75 volume percent or more inorganic nanoporous particles based on total article volume and having a density of 0.14 grams per cubic centimeter or less and a thermal conductivity of 25 milliWatts per meter*Kelvin or less and having a thickness of at least 0.5 centimeters.
  • Embodiments of the first aspect can include any one or combination of more than one of the following additional characteristics: the inorganic nanoporous particles being functionally free of organic components having latent covalent bonding reactivity and functional coatings over the outside of the particles and the article being functionally free of hollow non-porous particles, sheet silicates and clay minerals; having the inorganic nanoporous particles present at a concentration of 90 volume percent or more based on total article volume; having a thickness and sufficient flexibility to bend a plane perpendicular to the thickness at least 90 degrees around a mandrel having a diameter equal to the thickness of the article without macroscopic fracturing or crumbling; the water dispersible
  • polyurethane being thermoplastic aliphatic polyurethane; the water dispersible polyurethane containing a form of dimethylolpropionic acid; the water dispersible polyurethane is non- foamed; the water dispersible polyurethane is crosslinked; the inorganic nanoporous particles include aerogel particles that contain silicon dioxide; the inorganic nanoporous particles have pore walls that are sufficiently hydrophobic so as to preclude water absorption throughout the porous structure of the particles; being in the form of a plank that is at least two centimeters thick, fifteen centimeters wide and fifteen centimeters long; and comprising a facer on at least one surface of the article.
  • the present invention is process for preparing the article of the first aspect, the process comprising the following steps: (a) dispersing inorganic nanoporous particles into an aqueous dispersion of water dispersible polyurethane to form a filled dispersion; (b) casting the filled dispersion into a mold; and (c) drying to form an article of the first aspect.
  • Embodiments of the second aspect can further include any one or any combination of more than one of the following characteristics: the inorganic nanoporous particles are present in the filled dispersion at a concentration sufficient to result in 90 volume percent or more of the article volume of the final article volume; the water dispersible polyurethane is an aliphatic polyurethane; the water dispersible polyurethane contains a form of
  • the filled dispersion in step (b) is non-foamed; the water dispersible polyurethane after step (c) is crosslinked and the crosslinking is induced at any point or points prior to, during or after step (c); and the inorganic nanoporous particles have pore walls that are sufficiently hydrophobic so as to preclude water absorption throughout the porous structure of the particles.
  • the present invention is a method for using the article of the first aspect, the method of use comprising placing the article of the first aspect in a structure between two areas that can differ in temperature.
  • the process of the present invention is useful to prepare the article of the present invention.
  • the article of the present invention is useful as thermally an insulating material, particularly in applications where insulation having flexibility and low thermal conductivity is necessary, as well as for sound insulation (acoustical dampening).
  • Particular uses for the article of the present invention include pipe and tank insulation and acoustical attenuation (acoustical insulation) in applications such as appliance panels and building insulation.
  • Test methods refer to the most recent test method as of the priority date of this document unless the test method number includes a different date. References to test methods contain both a reference to the testing society and the test method number. The following test method abbreviations apply herein: ASTM refers to American Society for Testing and Materials; EN refers to European Norm; DIN refers to Irishs Institute fur Normung; and ISO refers to International Organization for Standards.
  • Length is a dimension having a magnitude equivalent to the largest magnitude dimension of the length, width and thickness. Thickness has a magnitude equal to the smallest magnitude of the length, width and thickness. Width has a magnitude equal to the length, thickness, both the length and thickness, or a magnitude somewhere between that of the length and thickness.
  • inorganic nanoporous particles that are functionally free of a coating means that there is no material effect on the physical properties of the article of the present invention containing the inorganic nanoporous particles due to the presence of the coating.
  • Nanoporous particles for use in the present invention include aerogel, xerogcl, cryogel, zeolite, dried alcogcl, and mesostructured cellular materials.
  • Nanoporous particles are particles that define pores within the particle that are less than one micron in average cross sectional diameter.
  • the nanoporous particles for use in the present invention have average pore cross sectional diameters of 500 nanometers (nm) or less, preferably 250 nm or less, still more preferably 100 nm or less and yet more preferably 70 nm or less.
  • the average pore cross sectional diameters of the nanoporous particles are 5 nm or more.
  • the inorganic nanoporous particles of the present invention are distinct from organic-inorganic hybrid aerogel particulates such as those disclosed in United States patent application US2010/0080949 because the inorganic nanoporous particles of the present invention are free of organic components having latent covalent bonding reactivity
  • the inorganic nanoporous materials in the present invention are in the form of
  • Particles bound together by a polyurethanc binder.
  • a “particle” as used herein refers to objects of any shape.
  • Particles of inorganic nanoporous materials for use in the present invention typically have a largest dimension that is in a range from five micrometers to five millimeters. Desirably, the largest particle dimension is 50 micrometers or larger, still more preferably 200 micrometers or large. At the same time, desirably the largest particle dimension is four millimeters or less, preferably two millimeters or less. In a particularly desirable embodiment use a broad particle size distribution, or particles having a multimodal (for example, bimodal or trimodal) particle size distribution to achieve a more dense packing of particles than is achievable with a narrow particle size distribution.
  • multimodal for example, bimodal or trimodal
  • Inorganic nanoporous particles make up a majority of the volume of an article of the present invention. Typically, inorganic nanoporous particles account for 75 percent by volume (vol%) or more of the article. Desirably, the inorganic nanoporous particles are present in an article of the present invention at a concentration of 85 vol% or more, preferably 90 vol% or more, still more preferably 95 vol% or more and can be present at a concentration of 98 vol% or more based on total article volume. Typically, the
  • concentration of nanoporous particles in the articles of the present invention is 99 vol% or less in order to ensure sufficient volume of binder to adhere the particles together.
  • Inorganic aerogel materials arc perhaps the most well known nanoporous materials that are suitable for use in the present invention.
  • Inorganic aerogel materials include those made of metallic oxides, such as silica, alumina, titania and ceria, as prepared from sol-gel techniques. Silicon (Si) or aluminum (Al) based aerogel composites are two such more commonly used materials.
  • a common and particularly desirable aerogel material for use as the nanoporous particles of the present invention are silicon dioxide (Si0 2 ) aerogels.
  • the nanoporous particles have a surface that can undergo hydrogen bonding with the water dispersible polyurethane binder used in the present invention.
  • the inorganic nanoporous particles are functionally free, and can be absolutely free of functional coatings.
  • Functional coatings form a coherent layer over or encapsulate an inorganic nanoporous particle and impart at least one chemical or physical property or characteristic to that surface that is different from the chemical and physical properties and characteristics of the pre-coated particle surface.
  • US2008/0287561 describes polymeric foams containing aerogel particles in a polymer matrix, but the aerogel particles comprise a functional coating that forms a cohesive barrier layer on the outer surface of the particles thereby preventing polymer from penetrating pores of the aerogel particles. Therefore, the aerogel particles of US2008/0287561 are not functionally free of functional coatings.
  • pore walls of the inorganic nanoporous particles have a sufficiently hydrophobic surface so as to preclude water absorption throughout the porous structure of the particles. If the pore walls of the particles are too hydrophilic, water from the binder composition can soak into the pore structure of the particle making drying of the final article difficult and can lead to collapse of the particle during drying due to the capillary force of water exiting the pore network. This does not necessarily require any coating or treatment on the outside surface of the particle itself, as is required in US2008/0287561 but rather a characteristic of the pore wall within the particles.
  • an inorganic nanoporous particle has such a sufficiently hydrophobic surface by subjecting a group of particles to a water bath for 30 minutes, drying the particles in a forced air oven at 80 °C for three hours and determining the amount of water remaining in the particles. If less than 15%, preferably less than 10%, more preferably less than 5%, still more preferably less than 2% of the weight of the dried particles corresponds to water then the pore walls of the particles have a sufficiently hydrophobic surface.
  • Articles of the present invention have nanoporous particles bound together using a water dispersible polyurethane binder. Typically, there is an absence of any covalent bonding between the polyurethane binder and the nanoporous particles.
  • Water dispersible polyurethane binder is not necessary redispersible in water, but rather the name refers to the form of the particular type of polyurethane prior to drying. Therefore, reference to water dispersible polyurethane binder in the context of the article of the present invention typically refers to a coalesced version of the binder as opposed to a dispersion, or even a redispersible form of the binder.
  • Reference to water dispersible polyurethane in the context of the process of the present invention prior to drying can refer to a form of the polyurethane that is dispersible or even dispersed in water (as the context will indicate).
  • the water dispersible polyurethane binder is typically non-foamed in the process and article of the present invention.
  • Water dispersible polyurethane is distinguishable from other forms of polyurethane due to the presence of functionality enabling dispersion of the polymer into water.
  • a particularly desirable form of water-dispersible polyurethane contains a form of
  • DMPA dimethylolpropionic acid
  • bis-MPA 2,2- bis(hydroxymethyl)propanoic acid
  • DMPA can be present in an acidic form or an anionic form. The anionic form is most desirable.
  • DMPA can be present in the polyurethane at a concentration of 0.2 wt% or more, preferably 0.5 wt% or more and can be present at a concentration of one wt% or more, four wt% or more or even five wt% or more based on total water dispersible polyurethane solids weight.
  • the concentration of DMPA is typically present at a concentration of 10 wt% or less based on total water dispersible polyurethane solids weight.
  • Exemplary guideline conditions for such an analysis use a Frontier Labs 202iD pyroloyzer to pyrolyze air dried sample at 650 °C for 12 seconds followed by separation of volatile pyrolysis products using an Agilent 6890 gas chromatograph equipped with a Supelco (SLB-5ms, 28746-U) separation column, using the following parameters: set temperature to 40 °C for one minute, 40 °C to 320 °C at 8 0 C per minute ramping rate, 320 0 C for 15 minutes; set column flow to 0.6 mL/min, pressure to 2.8 pounds per square inch. Identify separated components using a
  • Water dispersible polyurethanes are available as aqueous polyurethane dispersions, or "PUDs".
  • PUDs comprise water dispersible polyurethane in an aqueous carrier.
  • PUD systems including those with thermoplastic water dispersible polyurethane as well as thermosetting water dispersible polyurethane with cross-linkable polyurethane particles (either two-component systems or one-component systems with latent crosslinking moieties in the particles).
  • the present invention in its broadest scope, is not limited to a particular type of water dispersible polyurethane.
  • thermoplastic water dispersible polyurethanes are most desirable for preparing articles of the present invention, particularly flexible articles of the present invention.
  • thermoplastic polymer binders particularly at high levels of crosslinking. CrossHnking can occur before, during or after diying of the P UD by known methods including UV curing and use of chemical crosslinking agents. Aliphatic water dispersible polyurethanes are particularly desirable. The water dispersible polyurethane can be anionic to facilitate aqueous dispersibility.
  • Water dispersible polyurethane binder is a minor component by volume of the article of the present invention.
  • the water dispersible polyurethane binder is present at a concentration of 25 vol% or less, preferably 20 vol% or less, more preferably 15 vol% or less, still more preferably 10 vol% or less, most preferably 5 vol% or less and can be present at a concentration of two vol% or less based on total dried article volume.
  • the water dispersible polyurethane binder is present at a concentration of at least one vol% based on total dried article volume in order to ensure mechanical integrity of the article.
  • Articles of the present invention can contain any one or any combination of more than one of the following additives: fibers, colorant, flame retardant (for example, halogenated organic compounds, phosphorous compounds, and/or inorganic compounds), infrared attenuating agents (for example, carbon black and graphite, titanium dioxide), boron carbide, diatomite, manganese ferrite, manganese oxide, nickel oxide, tin oxide, silver oxide, bismuth oxide, titanium carbide, tungsten carbide, iron titanium oxide, zirconium silicate, zirconium oxide, iron(I) oxide, iron (III) oxide, manganese dioxide, manganese dioxide, iron titanium oxide (ilmenite), chromium oxide, silicon carbide, insecticides, fungicides, biocides, mildewcides and algaecides.
  • fibers for example, halogenated organic compounds, phosphorous compounds, and/or inorganic compounds
  • flame retardant for example, halogenated organic compounds, phosphorous compounds,
  • Articles of the present invention can also be free from any one or any combination of more than one of the stated additives.
  • the articles of the present invention can be free of fibers or, in particular, polyethylene terephthalate fibers.
  • Additives are generally present at a concentration of five vol% or less, two vol% or less, one vol% or less or zero vol% (absent) based on total article volume.
  • the articles are preferably functionally tree and can be completely free of hollow non-porous fillers, sheet silicates and clay minerals.
  • the density of articles of the present invention are affected by less than 0.01 grams per cubic centimeter (g/cm ), preferably less than 0.005 g/cm , more preferably less than 0.001 g/cm 3 due to the presence of hollow non-porous fillers as compared to the article density in an absence of the hollow non-porous fillers.
  • sheet silicates and clay minerals Being functionally free of sheet silicates and clay minerals means that the articles comprise less than 0.5 percent by weight (wt%), preferably less than 0.1 wt% and can be completely free of sheet silicates and clay minerals relative to inorganic nanoporous particle weight.
  • Sheet silicates and clay minerals assume their meaning from United States patent 5,656, 195 (incorporated herein by reference) and include montmorillonite, kaolinites and/or attapulgites.
  • Articles of the present invention have a density of 0.14 g/cm 3 or less, preferably 0.12 g/cm 3 or less and yet more preferably 0.10 g/cm 3 or less. Generally, the article will have a density of 0.01 g/cm 3 or higher to ensure desirable mechanical durability. Determine article density according to ASTM D1622.
  • Thermal conductivity is an important characteristic of the articles of the present invention.
  • the articles beneficially enjoy low conductivity properties due to the high volume of inorganic nanoporous particles.
  • Articles of the present invention have a thermal conductivity of 25 milliWatts per meter* elvin (mW/m*K) or less, preferably 24 mW7m*K or less, still more preferably 23 mW/m*K or less and can be 22 mW/m*K or less or even 21 mW/m*K or less. Determine article thermal conductivity according to ASTM C518.
  • Particularly desirable embodiments of the present invention are flexible.
  • Flexible articles of the present invention can be reversibly bent, compressed, or indented without fracturing. Flexibility is unusual for inorganic nanoporous articles.
  • One of the drawbacks to inorganic nanoporous materials such as aerogels is that they tend to be rigid and friable. Those characteristics make them undesirable for use in construction applications where flexible insulation such as fiber batt has historically been desirable.
  • use of a water dispersible polyurethane binder enables embodiments of the present invention to bend, compress and indent without macroscopic damage.
  • desirable embodiments of articles of the present invention can bend such that a plane of the article perpendicular to the thickness dimension of the article bends at least 90 degrees around a mandrel having a diameter equal to the thickness of the article without any macroscopic crumbling or fracturing of the article. This extent of flexibility far exceeds the 130 degree angle
  • Articles of the present invention are capable of efficient production in dimensions suitable for use in building and construction without the handicaps associated with trying to prepare an aerogel article in those same dimensions. Unlike manufacturing aerogel articles, manufacturing articles of the present invention does not include removal of large volumes of solvent from inorganic nanoporous structures. Articles of the present invention can have thicknesses of 0.5 centimeters (cm) or more, preferably 0.75 cm or more, still more preferably one cm or more, still more preferably 1.25 cm or more, and can have thickness of even 2.5 cm or more. At the same time, the articles having these thicknesses can have length and width dimensions that are 15 cm or more.
  • the article of the present invention can include one or more facer on one or more surface.
  • the article of the present invention includes a facer on opposing surfaces forming a sandwiched structure.
  • the article of the present invention can also, or
  • Suitable sheathing includes polymeric foam boards, oriented strand board, plaster board and gypsum board.
  • Prepare articles of the present invention by dispersing inorganic nanoporous particles into an aqueous dispersion of water dispersible polyurethane to form a filled dispersion; casting the filled dispersion into a mold; and drying to form an article of the present invention.
  • the inorganic nanoporous particles and water dispersible polyurethane are as described for the article of the present invention.
  • the filled dispersion can be foamed or non-foamed upon casting into a mold and can be free of polyethylene terephthalate fibers.
  • One desirable method of using the articles of the present invention is as thermally insulating materials.
  • the article serves to inhibit heat flow from one of the areas to the other and thereby provides thermal insulation.
  • areas that can differ in temperature include inside and outside of a refrigerator, inside and outside of a building structure (homes, office building, stores and the like), inside and outside of pipes, as well as inside and outside of spacecraft or other transportation vehicles.
  • Articles of the present invention have utility as, for example, insulating refrigerator panels, flexible pipe insulation, insulating sheathing materials for building and construction applications, and structural panel insulation.
  • the articles of the present invention offer insulation capability as thermal insulation, acoustical insulation, or both thermal and acoustical insulation.
  • the resulting article is an example of the present invention that is 15 cm by 15 cm by 2.5 cm in dimensions.
  • the article is capable of bending its 15 cm by 15 cm plane 90 °C around a 2.5 cm diameter mandrel without macroscopic fracturing or crumbling.
  • the article has a density of 0.087 g/cm 3 and a thermal conductivity of 20.8 mW/m*K.
  • the aerogel particles account for approximately 95.8 vol% of the final dried article while the binder accounts for 4.2 vol% of the final dried article.
  • the article is free of hollow non-porous particles and sheet silicates.
  • the binder is non-foamed.
  • NanogelTM Si0 2 aerogel particles have a maximum of 1.4% water by weight of the dried particles after subjecting a group of particles to a water bath for 30 minutes, drying the particles in a forced air oven at 80 °C for three hours and determining the amount of water remaining in the particles.

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  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

An article contains inorganic nanoporous particles bound together by water dispersible polyurethane, the article having 75 volume-percent or more inorganic nanoporous particles based on total article volume and having a density of 0.14 grams per cubic centimeter or less and a thermal conductivity of 25 milliWatts per meter*Kelvin or less and having a thickness of at least 0.5 centimeters. A process for preparing such an article includes dispersing inorganic nanoporous particles into an aqueous dispersion of dispersible polyurethane to form a dispersion, casting the dispersion into a mold, and drying to form an article. A method for using such an article includes placing the article in a structure between two areas that can differ in temperature.

Description

INORGANIC NANOPOROUS PARTICLES WITH WATER DISPERSIBLE
POLYURETHANE BINDER
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to an article of manufacture, a process for
manufacturing the article of manufacture and a method for using the article. The article of manufacture comprises inorganic nanoporous particles bound together with a water dispersible polyurethane binder.
Description of Related Art
Inorganic nanoporous materials such as aerogel materials offer tremendous thermal insulation properties. However, aerogel materials are not currently useful in building and construction applications due to cost and delicate mechanical properties. Preparing aerogel materials in a construction-sized solitary plank is currently not feasible, certainly not in the cost range of traditional insulating foam boards and planks. Part of the process for producing aerogels requires removing a large volume of solvent from the nanopore structure, typically by extraction with supercritical carbon dioxide in an autoclave or by other demanding drying methods. Such a process is formidable for a construction-sized solitary plank. Even so, aerogels tend to be friable and crumble to powder readily under abrasive force, which is common during handling on a construction site. Therefore, it is desirable to develop a plank of aerogel-like material that is less costly than casting a solitary aerogel plank and that is less friable than a solitary aerogel plank.
There have been numerous attempts at preparing aerogel containing insulating materials that are more amenable to construction applications than a solitary aerogel plank. For example, there are compositions that combine a polymeric foam matrix comprising an aerogel component. US2008/0287561 describes polymeric foams containing aerogel particles dispersed in the polymer matrix. The aerogel particles require a coating to prevent polymer from penetrating pores of the aerogel material. US 6,136,216 describes a composition of aerogel and gelatin that is foamed. The composition is shapcable into various shapes. US 5,137,927 describes a polystyrene foam containing aerogel particles dispersed therein. WO2007/146945 A2 describes flexible open cell foam/aerogel composites. In each of these references a foam binder contains aerogel particles.
Other technologies use a non-foamed binder to adhere aerogel particles together. US2010/0080949 describes using polymer/silica hybrid aerogel particles or beads covalently bonded with a binder to prepare aerogel composites. The aerogel particles of this invention are a hybrid of inorganic and organic materials. US 5,656,195 describes aerogel moldings that require 0.5 to 10 weight-percent sheet silicates and/or clay minerals based on aerogel weight to improve breaking strength. US2004/0077738 describes a layered insulation article that includes a component comprising aerogel, and aqueous binder and hollow non- porous particles presumably to reduce the density of the article.
Flexibility is desirable in an aerogel structure in addition to low density and thermal insulation properties, particularly for building and construction insulation applications where the insulating material may need to conform to various shapes in shipping, handling and application. The United States National Aeronautics and Space Administration has reported on recent developments on flexible crosslinked aerogel monolithic articles that comprise a polymerized and chemically bound coating over the aerogel structure (see publication LEW-18265-1 dated 04-06-09). Some degree of flexibility is also evident in articles of amine-modified aerogel monoliths crosslinked with di-isocyanate molecules (see, Capadona, et al., Polymer 47 (2006) 5754-5761). Both of these processes require casting a single aerogel monolithic crosslinked structure, a process that is a formidable task for construction-sized insulating articles.
A thermally insulating structure, particularly a flexible thermally insulating structure, comprising mostly inorganic nanoporous particles such as aerogel particles bonded together with a binder, but without a functional coating on the inorganic nanoporous particles is desirable. Still more desirable is such a structure that does not require a coating on the inorganic nanoporous particles, the presence of hollow non-porous particles or the presence of sheet silicates or clay minerals to achieve low density, flexibility and strength.
BRIEF SUMMARY OF THE INVENTION
It is an object of an embodiment of the present invention to provide a low density thermal insulating material that is made primarily of inorganic nanoporous particles, but that can be flexible, and that does not require a functional coating on inorganic nanoporous particles, the presence of hollow non-porous particles or the presence of sheet silicates or clay minerals to achieve flexibility and strength. It is also an objective of an embodiment of the present invention to achieve the aforementioned objectives with a non-foamed binder.
Surprisingly, the present invention provides a solution to this objective by forming an article of inorganic nanoporous particles using water dispersible polyurethane as a binder for inorganic nanoporous particles.
In a first aspect, the present invention is an article comprising inorganic nanoporous particles bound together by water dispersible polyurethane, the article comprising 75 volume percent or more inorganic nanoporous particles based on total article volume and having a density of 0.14 grams per cubic centimeter or less and a thermal conductivity of 25 milliWatts per meter*Kelvin or less and having a thickness of at least 0.5 centimeters.
Embodiments of the first aspect can include any one or combination of more than one of the following additional characteristics: the inorganic nanoporous particles being functionally free of organic components having latent covalent bonding reactivity and functional coatings over the outside of the particles and the article being functionally free of hollow non-porous particles, sheet silicates and clay minerals; having the inorganic nanoporous particles present at a concentration of 90 volume percent or more based on total article volume; having a thickness and sufficient flexibility to bend a plane perpendicular to the thickness at least 90 degrees around a mandrel having a diameter equal to the thickness of the article without macroscopic fracturing or crumbling; the water dispersible
polyurethane being thermoplastic aliphatic polyurethane; the water dispersible polyurethane containing a form of dimethylolpropionic acid; the water dispersible polyurethane is non- foamed; the water dispersible polyurethane is crosslinked; the inorganic nanoporous particles include aerogel particles that contain silicon dioxide; the inorganic nanoporous particles have pore walls that are sufficiently hydrophobic so as to preclude water absorption throughout the porous structure of the particles; being in the form of a plank that is at least two centimeters thick, fifteen centimeters wide and fifteen centimeters long; and comprising a facer on at least one surface of the article.
In a second aspect, the present invention is process for preparing the article of the first aspect, the process comprising the following steps: (a) dispersing inorganic nanoporous particles into an aqueous dispersion of water dispersible polyurethane to form a filled dispersion; (b) casting the filled dispersion into a mold; and (c) drying to form an article of the first aspect.
Embodiments of the second aspect can further include any one or any combination of more than one of the following characteristics: the inorganic nanoporous particles are present in the filled dispersion at a concentration sufficient to result in 90 volume percent or more of the article volume of the final article volume; the water dispersible polyurethane is an aliphatic polyurethane; the water dispersible polyurethane contains a form of
dimethylolpropionic acid; the filled dispersion in step (b) is non-foamed; the water dispersible polyurethane after step (c) is crosslinked and the crosslinking is induced at any point or points prior to, during or after step (c); and the inorganic nanoporous particles have pore walls that are sufficiently hydrophobic so as to preclude water absorption throughout the porous structure of the particles.
In a third aspect, the present invention is a method for using the article of the first aspect, the method of use comprising placing the article of the first aspect in a structure between two areas that can differ in temperature.
The process of the present invention is useful to prepare the article of the present invention. The article of the present invention is useful as thermally an insulating material, particularly in applications where insulation having flexibility and low thermal conductivity is necessary, as well as for sound insulation (acoustical dampening). Particular uses for the article of the present invention include pipe and tank insulation and acoustical attenuation (acoustical insulation) in applications such as appliance panels and building insulation.
DETAILED DESCRIPTION OF THE INVENTION
Test methods refer to the most recent test method as of the priority date of this document unless the test method number includes a different date. References to test methods contain both a reference to the testing society and the test method number. The following test method abbreviations apply herein: ASTM refers to American Society for Testing and Materials; EN refers to European Norm; DIN refers to Deutsches Institute fur Normung; and ISO refers to International Organization for Standards.
"Multiple" means two or more. "And/or" means "and, or as an alternative". All ranges include endpoints unless otherwise indicated.
"Length", "width" and "thickness" are three mutually perpendicular dimensions of an article. Length is a dimension having a magnitude equivalent to the largest magnitude dimension of the length, width and thickness. Thickness has a magnitude equal to the smallest magnitude of the length, width and thickness. Width has a magnitude equal to the length, thickness, both the length and thickness, or a magnitude somewhere between that of the length and thickness.
"Functionally free" means that, if present, the concentration is below that whi ch would have a material effect on the physical properties of the article of the present invention, unless otherwise specifically defined herein. For example, inorganic nanoporous particles that are functionally free of a coating means that there is no material effect on the physical properties of the article of the present invention containing the inorganic nanoporous particles due to the presence of the coating. Within the scope of the definition of
"functionally free" is "free of (meaning absent).
Inorganic nanoporous particles for use in the present invention include aerogel, xerogcl, cryogel, zeolite, dried alcogcl, and mesostructured cellular materials. Nanoporous particles are particles that define pores within the particle that are less than one micron in average cross sectional diameter. Desirably, the nanoporous particles for use in the present invention have average pore cross sectional diameters of 500 nanometers (nm) or less, preferably 250 nm or less, still more preferably 100 nm or less and yet more preferably 70 nm or less. Typically, the average pore cross sectional diameters of the nanoporous particles are 5 nm or more. Determine average pore cross sectional diameters of the nanoporous particles using calculations according to the Brunauer-Emmett-Teller (BET) technique with desorption curve data collected using the method of Barrett- Joyner-Henda (see, K.S.W.Sing et al, Pure & Appl. Chem., Vol. 57, No. 4, pp. 603-619 (1985)). Pore size and isotherm classification follow IUPAC standards.
The inorganic nanoporous particles of the present invention are distinct from organic-inorganic hybrid aerogel particulates such as those disclosed in United States patent application US2010/0080949 because the inorganic nanoporous particles of the present invention are free of organic components having latent covalent bonding reactivity
(reactivity susceptible to covalent bond formation) and are desirably free of organic components altogether.
The inorganic nanoporous materials in the present invention are in the form of
"particles" bound together by a polyurethanc binder. A "particle" as used herein refers to objects of any shape. Particles of inorganic nanoporous materials for use in the present invention typically have a largest dimension that is in a range from five micrometers to five millimeters. Desirably, the largest particle dimension is 50 micrometers or larger, still more preferably 200 micrometers or large. At the same time, desirably the largest particle dimension is four millimeters or less, preferably two millimeters or less. In a particularly desirable embodiment use a broad particle size distribution, or particles having a multimodal (for example, bimodal or trimodal) particle size distribution to achieve a more dense packing of particles than is achievable with a narrow particle size distribution.
Inorganic nanoporous particles make up a majority of the volume of an article of the present invention. Typically, inorganic nanoporous particles account for 75 percent by volume (vol%) or more of the article. Desirably, the inorganic nanoporous particles are present in an article of the present invention at a concentration of 85 vol% or more, preferably 90 vol% or more, still more preferably 95 vol% or more and can be present at a concentration of 98 vol% or more based on total article volume. Typically, the
concentration of nanoporous particles in the articles of the present invention is 99 vol% or less in order to ensure sufficient volume of binder to adhere the particles together.
Inorganic aerogel materials arc perhaps the most well known nanoporous materials that are suitable for use in the present invention. Inorganic aerogel materials include those made of metallic oxides, such as silica, alumina, titania and ceria, as prepared from sol-gel techniques. Silicon (Si) or aluminum (Al) based aerogel composites are two such more commonly used materials. A common and particularly desirable aerogel material for use as the nanoporous particles of the present invention are silicon dioxide (Si02) aerogels. In one embodiment, the nanoporous particles have a surface that can undergo hydrogen bonding with the water dispersible polyurethane binder used in the present invention.
The inorganic nanoporous particles are functionally free, and can be absolutely free of functional coatings. Functional coatings form a coherent layer over or encapsulate an inorganic nanoporous particle and impart at least one chemical or physical property or characteristic to that surface that is different from the chemical and physical properties and characteristics of the pre-coated particle surface. For example, US2008/0287561 describes polymeric foams containing aerogel particles in a polymer matrix, but the aerogel particles comprise a functional coating that forms a cohesive barrier layer on the outer surface of the particles thereby preventing polymer from penetrating pores of the aerogel particles. Therefore, the aerogel particles of US2008/0287561 are not functionally free of functional coatings.
Desirably, pore walls of the inorganic nanoporous particles have a sufficiently hydrophobic surface so as to preclude water absorption throughout the porous structure of the particles. If the pore walls of the particles are too hydrophilic, water from the binder composition can soak into the pore structure of the particle making drying of the final article difficult and can lead to collapse of the particle during drying due to the capillary force of water exiting the pore network. This does not necessarily require any coating or treatment on the outside surface of the particle itself, as is required in US2008/0287561 but rather a characteristic of the pore wall within the particles. Determine if an inorganic nanoporous particle has such a sufficiently hydrophobic surface by subjecting a group of particles to a water bath for 30 minutes, drying the particles in a forced air oven at 80 °C for three hours and determining the amount of water remaining in the particles. If less than 15%, preferably less than 10%, more preferably less than 5%, still more preferably less than 2% of the weight of the dried particles corresponds to water then the pore walls of the particles have a sufficiently hydrophobic surface.
Articles of the present invention have nanoporous particles bound together using a water dispersible polyurethane binder. Typically, there is an absence of any covalent bonding between the polyurethane binder and the nanoporous particles. "Water dispersible polyurethane binder" is not necessary redispersible in water, but rather the name refers to the form of the particular type of polyurethane prior to drying. Therefore, reference to water dispersible polyurethane binder in the context of the article of the present invention typically refers to a coalesced version of the binder as opposed to a dispersion, or even a redispersible form of the binder. Reference to water dispersible polyurethane in the context of the process of the present invention prior to drying can refer to a form of the polyurethane that is dispersible or even dispersed in water (as the context will indicate). The water dispersible polyurethane binder is typically non-foamed in the process and article of the present invention.
Water dispersible polyurethane is distinguishable from other forms of polyurethane due to the presence of functionality enabling dispersion of the polymer into water. A particularly desirable form of water-dispersible polyurethane contains a form of
dimethylolpropionic acid (DMPA), which is also known as 2,2- bis(hydroxymethyl)propanoic acid (bis-MPA). DMPA can be present in an acidic form or an anionic form. The anionic form is most desirable. DMPA can be present in the polyurethane at a concentration of 0.2 wt% or more, preferably 0.5 wt% or more and can be present at a concentration of one wt% or more, four wt% or more or even five wt% or more based on total water dispersible polyurethane solids weight. At the same time, the concentration of DMPA is typically present at a concentration of 10 wt% or less based on total water dispersible polyurethane solids weight.
Determine the presence of DMPA using pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS) by looking for fragments of isobutene, 2-methyl-2- proprene-l -ol and methacrylic acid in the mass spectrum. Exemplary guideline conditions for such an analysis use a Frontier Labs 202iD pyroloyzer to pyrolyze air dried sample at 650 °C for 12 seconds followed by separation of volatile pyrolysis products using an Agilent 6890 gas chromatograph equipped with a Supelco (SLB-5ms, 28746-U) separation column, using the following parameters: set temperature to 40 °C for one minute, 40 °C to 320 °C at 80 C per minute ramping rate, 3200 C for 15 minutes; set column flow to 0.6 mL/min, pressure to 2.8 pounds per square inch. Identify separated components using a
ThermoElectron DSQ quadrupole mass spectrometer by comparison with mass spectra from the National Institute of Standards and Technology database. Use the following parameters: scan rate of two scans per second, san mode is mass scan range: 14-600; electron ionization (EI Volume); Detector gain - 2Xe5; MS acquisition time = 1 minute; emission Current = 70 microamperes; and source current equals 325 microamperes. A skilled artisan can optimize these guideline parameters as needed for their equipment and conditions.
Water dispersible polyurethanes are available as aqueous polyurethane dispersions, or "PUDs". PUDs comprise water dispersible polyurethane in an aqueous carrier. There are many types of PUD systems including those with thermoplastic water dispersible polyurethane as well as thermosetting water dispersible polyurethane with cross-linkable polyurethane particles (either two-component systems or one-component systems with latent crosslinking moieties in the particles). The present invention, in its broadest scope, is not limited to a particular type of water dispersible polyurethane. However, thermoplastic water dispersible polyurethanes are most desirable for preparing articles of the present invention, particularly flexible articles of the present invention. It can be advantageous to induce some level of crosslinking, particularly when using a polyurethane having a particularly low glass transition temperature in order to enhance mechanical integrity in the final article. However, excessive crosslinking in a binder will reduce flexibility of the final article. Thermosetting polymer binders are crosslinked and so tend to produce less flexible articles than
thermoplastic polymer binders, particularly at high levels of crosslinking. CrossHnking can occur before, during or after diying of the P UD by known methods including UV curing and use of chemical crosslinking agents. Aliphatic water dispersible polyurethanes are particularly desirable. The water dispersible polyurethane can be anionic to facilitate aqueous dispersibility.
Water dispersible polyurethane binder is a minor component by volume of the article of the present invention. Typically the water dispersible polyurethane binder is present at a concentration of 25 vol% or less, preferably 20 vol% or less, more preferably 15 vol% or less, still more preferably 10 vol% or less, most preferably 5 vol% or less and can be present at a concentration of two vol% or less based on total dried article volume. Desirably, the water dispersible polyurethane binder is present at a concentration of at least one vol% based on total dried article volume in order to ensure mechanical integrity of the article.
Articles of the present invention can contain any one or any combination of more than one of the following additives: fibers, colorant, flame retardant (for example, halogenated organic compounds, phosphorous compounds, and/or inorganic compounds), infrared attenuating agents (for example, carbon black and graphite, titanium dioxide), boron carbide, diatomite, manganese ferrite, manganese oxide, nickel oxide, tin oxide, silver oxide, bismuth oxide, titanium carbide, tungsten carbide, iron titanium oxide, zirconium silicate, zirconium oxide, iron(I) oxide, iron (III) oxide, manganese dioxide, manganese dioxide, iron titanium oxide (ilmenite), chromium oxide, silicon carbide, insecticides, fungicides, biocides, mildewcides and algaecides. Articles of the present invention can also be free from any one or any combination of more than one of the stated additives. For example, the articles of the present invention can be free of fibers or, in particular, polyethylene terephthalate fibers. Additives are generally present at a concentration of five vol% or less, two vol% or less, one vol% or less or zero vol% (absent) based on total article volume.
The articles are preferably functionally tree and can be completely free of hollow non-porous fillers, sheet silicates and clay minerals. By being "functionally free" of hollow non-porous fillers the density of articles of the present invention are affected by less than 0.01 grams per cubic centimeter (g/cm ), preferably less than 0.005 g/cm , more preferably less than 0.001 g/cm3 due to the presence of hollow non-porous fillers as compared to the article density in an absence of the hollow non-porous fillers. Being functionally free of sheet silicates and clay minerals means that the articles comprise less than 0.5 percent by weight (wt%), preferably less than 0.1 wt% and can be completely free of sheet silicates and clay minerals relative to inorganic nanoporous particle weight. Sheet silicates and clay minerals assume their meaning from United States patent 5,656, 195 (incorporated herein by reference) and include montmorillonite, kaolinites and/or attapulgites.
Articles of the present invention have a density of 0.14 g/cm3 or less, preferably 0.12 g/cm3 or less and yet more preferably 0.10 g/cm3 or less. Generally, the article will have a density of 0.01 g/cm3 or higher to ensure desirable mechanical durability. Determine article density according to ASTM D1622.
Thermal conductivity is an important characteristic of the articles of the present invention. The articles beneficially enjoy low conductivity properties due to the high volume of inorganic nanoporous particles. Articles of the present invention have a thermal conductivity of 25 milliWatts per meter* elvin (mW/m*K) or less, preferably 24 mW7m*K or less, still more preferably 23 mW/m*K or less and can be 22 mW/m*K or less or even 21 mW/m*K or less. Determine article thermal conductivity according to ASTM C518.
Particularly desirable embodiments of the present invention are flexible. "Flexible" articles of the present invention can be reversibly bent, compressed, or indented without fracturing. Flexibility is unusual for inorganic nanoporous articles. One of the drawbacks to inorganic nanoporous materials such as aerogels is that they tend to be rigid and friable. Those characteristics make them undesirable for use in construction applications where flexible insulation such as fiber batt has historically been desirable. However, use of a water dispersible polyurethane binder enables embodiments of the present invention to bend, compress and indent without macroscopic damage. In fact, desirable embodiments of articles of the present invention can bend such that a plane of the article perpendicular to the thickness dimension of the article bends at least 90 degrees around a mandrel having a diameter equal to the thickness of the article without any macroscopic crumbling or fracturing of the article. This extent of flexibility far exceeds the 130 degree angle
(corresponding to a 50 degree bend) of Capadona et al. (Polymer 47 (2006) 5754-5761), the article disclosing flexible crosslinked silica aerogel monoliths using amine functionalized aerogel crosslinked with di-isocyanate molecules. Flexibility makes articles of the present invention particularly desirable for conforming to pipes and tanks in pipe and tank insulation applications and for conforming to cavities in cavity insulation applications.
Articles of the present invention are capable of efficient production in dimensions suitable for use in building and construction without the handicaps associated with trying to prepare an aerogel article in those same dimensions. Unlike manufacturing aerogel articles, manufacturing articles of the present invention does not include removal of large volumes of solvent from inorganic nanoporous structures. Articles of the present invention can have thicknesses of 0.5 centimeters (cm) or more, preferably 0.75 cm or more, still more preferably one cm or more, still more preferably 1.25 cm or more, and can have thickness of even 2.5 cm or more. At the same time, the articles having these thicknesses can have length and width dimensions that are 15 cm or more.
It is within the scope of the present invention to combine a facer such as metal sheet, film or foil, paper facer, a non-woven sheet facer, a fibrous facer sheet or some other facer to at least one surface of an article of the present invention. Hence, the article of the present invention can include one or more facer on one or more surface. In one particular embodiment, the article of the present invention includes a facer on opposing surfaces forming a sandwiched structure. The article of the present invention can also, or
alternatively, include one or more panel or plank of sheathing on one or more surface.
Examples of suitable sheathing includes polymeric foam boards, oriented strand board, plaster board and gypsum board.
Prepare articles of the present invention by dispersing inorganic nanoporous particles into an aqueous dispersion of water dispersible polyurethane to form a filled dispersion; casting the filled dispersion into a mold; and drying to form an article of the present invention. The inorganic nanoporous particles and water dispersible polyurethane are as described for the article of the present invention. The filled dispersion can be foamed or non-foamed upon casting into a mold and can be free of polyethylene terephthalate fibers.
One desirable method of using the articles of the present invention is as thermally insulating materials. In an embodiment of this method, place the article in a structure between two areas that can differ in temperature. The article serves to inhibit heat flow from one of the areas to the other and thereby provides thermal insulation. Examples of areas that can differ in temperature include inside and outside of a refrigerator, inside and outside of a building structure (homes, office building, stores and the like), inside and outside of pipes, as well as inside and outside of spacecraft or other transportation vehicles.
Articles of the present invention have utility as, for example, insulating refrigerator panels, flexible pipe insulation, insulating sheathing materials for building and construction applications, and structural panel insulation. The articles of the present invention offer insulation capability as thermal insulation, acoustical insulation, or both thermal and acoustical insulation.
Example
Combine in a beaker 60 milliliters of PRIMAL™ BINDER U91 aliphatic polyurethane dispersion that is 38.0-42.0 percent solids (PRIMAL is a trademark of the Rohm and Hass Company and that contains approximately 4 wt% DMPA based on solids weight and 39.6 grams of Nanogel™ Si02 aerogel particles (Nanogel is a trademark of Cabot Corporation) by slowly adding the aerogel particles to the polyurethane dispersion. The aerogel particles have an average size of 0.7 to 1.2 millimeters and average pore sizes of 20-40 nanometers and are functionally free of organic components having latent covalent bonding reactivity and functional coatings. Stir the mixture for approximately 20 minutes and then pour the mixture into a polytetrafluoroethylene-covered frame that is 15 em wide, 15 cm long and 2.5 cm deep. Place the frame and mixture in an oven at 80 °C for approximately three hours to dry.
The resulting article is an example of the present invention that is 15 cm by 15 cm by 2.5 cm in dimensions. The article is capable of bending its 15 cm by 15 cm plane 90 °C around a 2.5 cm diameter mandrel without macroscopic fracturing or crumbling. The article has a density of 0.087 g/cm3 and a thermal conductivity of 20.8 mW/m*K. The aerogel particles account for approximately 95.8 vol% of the final dried article while the binder accounts for 4.2 vol% of the final dried article. The article is free of hollow non-porous particles and sheet silicates. The binder is non-foamed.
The Nanogel™ Si02 aerogel particles have a maximum of 1.4% water by weight of the dried particles after subjecting a group of particles to a water bath for 30 minutes, drying the particles in a forced air oven at 80 °C for three hours and determining the amount of water remaining in the particles.

Claims

CLAIMS:
1. An article comprising inorganic nanoporous particles bound together by water dispersible polyurethane, the article comprising 75 volume percent or more inorganic nanoporous particles based on total article volume and having a density of 0.14 grams per cubic centimeter or less and a thermal conductivity of 25 milliWatts per meter*Kelvin or less and having a thickness of at least 0.5 centimeters.
2. The article of Claim 1 , further characterized by the inorganic nanoporous particles being functionally free of organic components having latent covalent bonding reactivity and functional coatings over the outside of the particles and the article being functionally free of hollow non-porous particles, sheet silicates and clay minerals.
3. The article of Claim 1, further characterized by having the inorganic nanoporous particles present at a concentration of 90 volume percent or more based on total article volume.
4. The article of Claim 1, further characterized by having a thickness and sufficient flexibility to bend a plane perpendicular to the thickness at least 90 degrees around a mandrel having a diameter equal to the thickness of the article without
macroscopic fracturing or crumbling.
5. The article of Claim 1, further characterized by the water dispersible polyurethane being thermoplastic aliphatic polyurethane.
6. The article of Claim 1 , further characterized by the water dispersible polyurethane containing a form of dimethylolpropionic acid.
7. The article of Claim 1 , wherein the water dispersible polyurethane is non- foamed.
8. The article of Claim 1, wherein the water dispersible polyurethane is crosslinked.
9. The article of Claim 1 , wherein the inorganic nanoporous particles include aerogel particles that contain silicon dioxide.
10. The article of Claim 1, wherein the inorganic nanoporous particles have pore walls that are sufficiently hydrophobic so as to preclude water absorption throughout the porous structure of the particles.
1 1. The article of Claim 1 , further characterized as being in the form of a plank that is at least two centimeters thick, fifteen centimeters wide and fifteen centimeters long.
12. The article of claim 1, further comprising a facer on at least one surface of the article.
13. A process for preparing the article of Claim 1, the process comprising the following steps: (a) dispersing inorganic nanoporous particles into an aqueous dispersion of water dispersible polyurethane to form a filled dispersion; (b) easting the filled dispersion into a mold; and (c) drying to form an article of Claim I .
14. The process of Claim 13, wherein the inorganic nanoporous particles are present in the filled dispersion at a concentration sufficient to result in 90 volume percent or more of the article volume of the final article volume.
15. The process of Claim 13, wherein the water dispersible polyurethane is an aliphatic polyurethane.
16. The process of Claim 13, wherein the water dispersible polyurethane contains a form of dimethylolpropionic acid.
17. The process of Claim 13, wherein the filled dispersion in step (b) is non- foamed.
18. The process of Claim 13, wherein the water dispersible polyurethane after step (c) is crosslinked and the crosslinking is induced at any point or points prior to, during or after step (c).
19. The process of Claim 13, wherein the inorganic nanoporous particles have pore walls that are sufficiently hydrophobic so as to preclude water absorption throughout the porous structure of the particles.
20. A method for using the article of Claim 1, the method of use comprising placing the article in a structure between two areas that can differ in temperature.
PCT/CN2010/074811 2010-06-30 2010-06-30 Inorganic nanoporous particles with water dispersible polyurethane binder WO2012000184A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CA2801139A CA2801139A1 (en) 2010-06-30 2010-06-30 Inorganic nanoporous particles with water dispersible polyurethane binder
ES10853889.3T ES2549166T3 (en) 2010-06-30 2010-06-30 Inorganic nanoporous particles with water dispersible polyurethane binder
PCT/CN2010/074811 WO2012000184A1 (en) 2010-06-30 2010-06-30 Inorganic nanoporous particles with water dispersible polyurethane binder
EP10853889.3A EP2588517B1 (en) 2010-06-30 2010-06-30 Inorganic nanoporous particles with water dispersible polyurethane binder
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EP2588517A1 (en) 2013-05-08
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ES2549166T3 (en) 2015-10-23
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US20130091682A1 (en) 2013-04-18
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RU2013103804A (en) 2014-08-10
CA2801139A1 (en) 2012-01-05

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