WO2019212460A1 - Mousse polymère comprenant de la cellulose nanocristalline - Google Patents

Mousse polymère comprenant de la cellulose nanocristalline Download PDF

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Publication number
WO2019212460A1
WO2019212460A1 PCT/US2018/030108 US2018030108W WO2019212460A1 WO 2019212460 A1 WO2019212460 A1 WO 2019212460A1 US 2018030108 W US2018030108 W US 2018030108W WO 2019212460 A1 WO2019212460 A1 WO 2019212460A1
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Prior art keywords
polymer foam
polymer
nano
crystalline cellulose
foam
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PCT/US2018/030108
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English (en)
Inventor
Venkata S. Nagarajan
Xiangmin Han
Yadollah Delaviz
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Owens Corning Intellectual Capital, Llc
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Priority to PCT/US2018/030108 priority Critical patent/WO2019212460A1/fr
Publication of WO2019212460A1 publication Critical patent/WO2019212460A1/fr

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/20—Ternary blends of expanding agents
    • C08J2203/202—Ternary blends of expanding agents of physical blowing agents
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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
    • C08J2325/00—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
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose

Definitions

  • the present disclosure relates to polymer foams, and more particularly, to polymer foams that include nano-crystalline cellulose, which exhibit improved water vapor permeability and reduced thermal conductivity.
  • Polymer foams are useful in a wide variety of applications such as thermal insulation, in cushions, as packaging, and as adsorbents.
  • Extruded polymer foams are generally made by melting a polymer together with any desired additives to create a polymer melt.
  • a blowing agent is mixed with the polymer melt at an appropriate temperature and pressure to produce a foamable gel mixture.
  • the foamable gel mixture is then cooled and extruded into a zone of reduced pressure, which results in a foaming of the gel and the formation of the desired extruded polymer foam product.
  • thermal insulation it is desirable to minimize the thermal conductivity of the polymer foam to improve the insulating capability of the polymer foam, and to control the water vapor permeability of the polymer foam to reduce the risk of mold growth due to moisture condensation and/or accumulation.
  • compositions for forming polymer foams include nano-crystalline cellulose, which reduces the thermal conductivity and improves the water vapor permeability of the polymer foams.
  • nano-crystalline cellulose which reduces the thermal conductivity and improves the water vapor permeability of the polymer foams.
  • a polymer foam is provided.
  • the polymer foam is formed from a composition that includes a polymer, 2% to 10% by weight nano- crystalline cellulose based on the total weight of the polymer foam, and at least one blowing agent.
  • the polymer foam exhibits a reduced thermal conductivity (k-value) and a higher water vapor permeability as compared to a comparative polymer foam without nano crystalline cellulose.
  • a composition for forming a polymer foam includes a polymer, 2% to 10% by weight nano-crystalline cellulose based on the total weight of the solids of the composition, and at least one blowing agent.
  • a polymer foam composition includes an alkenyl aromatic polymer and 2% to 10% by weight nano-crystalline cellulose based on the total weight of the polymer foam composition.
  • the polymer foam composition When the polymer foam composition is formed as a foam, the polymer foam exhibits a reduced thermal conductivity and a higher water vapor permeability as compared to a comparative polymer foam without nano-crystalline cellulose.
  • a method of making a polymer foam includes preparing a polymer melt comprising a polymer and nano crystalline cellulose, incorporating at least one blowing agent into the polymer melt to form a foamable mixture, and extruding the foamable mixture through a die into a region of reduced pressure to form the polymer foam.
  • the polymer foam exhibits a reduced thermal conductivity (k-value) and a higher water vapor permeability as compared to a comparative polymer foam without nano-crystalline cellulose.
  • FIG. 1 is a schematic drawing of an exemplary extrusion apparatus useful for making a polymer foam as described herein;
  • FIG. 2 is a graph of thermal conductivity (k-value) at 30 days aging for various extruded polystyrene foams as described in the Examples section herein;
  • FIG. 3 is a graph of the water vapor permeability for various extruded polystyrene foams as described in the Examples section herein. DETAILED DESCRIPTION
  • a polymer foam includes nano-crystalline cellulose, which provides the polymer foam with a reduced thermal conductivity and a higher water vapor permeability as compared to a comparative polymer foam that does not include nano-crystalline cellulose. While the present disclosure describes certain embodiments of the polymer foam, the composition for forming the polymer foam, and the method of making the polymer foam in detail, the present disclosure is to be considered exemplary and is not intended to be limited to the disclosed embodiments.
  • Numerical ranges as used herein are intended to include every number and subset of numbers within that range, whether specifically disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range. For example, a disclosure of 1 to 10 should be construed as supporting a range of 2 to 8, 3 to 7, 5 to 6, 1 to 9, 3.6 to 4.6, 3.5 to 9.9, and so forth.
  • the present disclosure relates to a composition and method of making a polymer foam that includes nano-crystalline cellulose to achieve a polymer foam that exhibits increased water vapor permeability and reduced thermal conductivity as compared to an otherwise identical polymer foam that does not include nano-crystalline cellulose. It was discovered that nano-crystalline cellulose, when incorporated in sufficient amounts into a polymer foam, functions as an infrared attenuating agent to reduce thermal conductivity and also improves the breathability of the polymer foam by increasing the water vapor permeability of the polymer foam.
  • a composition for forming a polymer foam comprises a polymer, 2% to 10% by weight nano-crystalline cellulose based on the total weight of the solids of the composition, and at least one blowing agent.
  • the composition for forming a polymer foam may further include one or more additives to improve the processing of the composition or the functionality of the resulting polymer foam.
  • the polymer is the backbone of the composition for forming the polymer foam and provides strength, flexibility, toughness, and durability to the final polymer foam product.
  • the polymer that may be used in the composition is not particularly limited, and generally, any polymer capable of being foamed may be used as the polymer in the exemplary compositions described herein.
  • the polymer may be thermoplastic or thermoset.
  • the polymer used in the composition may be selected to provide sufficient mechanical strength to the resulting polymer foam, or may be selected based on the process used to form the polymer foam.
  • the polymer is preferably chemically stable, that is, generally non-reactive, within the expected temperature range during formation and subsequent use of the resulting polymer foam.
  • polymer is generic to the terms“homopolymer,”
  • copolymer “terpolymer,” and combinations of homopolymers, copolymers, and/or terpolymers.
  • suitable polymers include alkenyl aromatic polymers, polyvinyl chloride (“PVC”), chlorinated polyvinyl chloride (“CPVC”), polyethylene, polypropylene, polycarbonates, polyisocyanurates, polyetherimides, polyamides, polyesters, polycarbonates, polymethylmethacrylate, polyphenylene oxide, polyurethanes, phenolics, polyolefins, styrene acrylonitrile (“SAN”), acrylonitrile butadiene styrene, acrylic/styrene/acrylonitrile block terpolymer (“ASA”), polysulfone, polyphenylene sulfide, acetal resins, polyaramides, polyimides, polyacrylic acid esters, copolymers of ethylene and propylene, copoly
  • the polymer is an alkenyl aromatic polymer.
  • alkenyl aromatic polymers include, but are not limited to, alkenyl aromatic homopolymers and copolymers of alkenyl aromatic compounds and copolymerizable ethylenically unsaturated co-monomers.
  • the alkenyl aromatic polymer may include minor proportions (e.g., less than 10% by weight) of non-alkenyl aromatic polymers.
  • the alkenyl aromatic polymer may be formed of one or more alkenyl aromatic homopolymers, one or more alkenyl aromatic copolymers, a blend of one or more of each of alkenyl aromatic homopolymers and copolymers, or blends thereof with a non-alkenyl aromatic polymer.
  • the alkenyl aromatic polymer comprises at least 50% by weight alkenyl aromatic monomer units.
  • the alkenyl aromatic polymer comprises at least 70% by weight alkenyl aromatic monomer units, including at least 80% by weight alkenyl aromatic monomer units, at least 90% by weight alkenyl aromatic monomer units, and also including at least 95% by weight alkenyl aromatic monomer units.
  • the alkenyl aromatic polymer is comprised entirely of alkenyl aromatic monomeric units.
  • alkenyl aromatic polymers examples include, but are not limited to, alkenyl aromatic polymers derived from alkenyl aromatic monomers such as styrene, alpha-methylstyrene, ethylstyrene, vinyl toluene, chlorostyrene, and bromostyrene.
  • alkenyl aromatic polymer used in the compositions described herein is polystyrene.
  • minor amounts e.g, less than 10% by weight of monoethylenically unsaturated monomers such as C2 to C6 alkyl acids and esters, ionomeric derivatives, and C2 to C6 dienes may be copolymerized with alkenyl aromatic monomers to form the alkenyl aromatic polymer.
  • monoethylenically unsaturated monomers such as C2 to C6 alkyl acids and esters, ionomeric derivatives, and C2 to C6 dienes may be copolymerized with alkenyl aromatic monomers to form the alkenyl aromatic polymer.
  • Non-limiting examples of such copolymerizable monomers include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, acrylonitrile, maleic anhydride, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, vinyl acetate, and butadiene.
  • the polymer of the composition comprises at least 90% by weight polystyrene. In certain exemplary embodiments, the polymer of the composition consists of polystyrene. In certain exemplary embodiments, the composition for forming a polymer foam comprises from 60% to 98% by weight polymer, including from 75% to 98% by weight polymer, from 85% to 98% by weight polymer, from 90% to 98% by weight polymer, and also including from 92% to 96% by weight polymer.
  • the exemplary composition for forming a polymer foam comprises from 2% to 10% by weight nano-crystalline cellulose based on the total weight of the solids of the composition.
  • Nano-crystalline cellulose may be obtained from the acid hydrolysis of cellulose fibers.
  • the nano-crystalline cellulose may be sourced from a variety of materials (e.g ., plants microorganisms, algae, sea animals) including, but not limited to, wood pulp, cotton, ramie, hemp, flax, sisal, wheat, straw, palm, sugar beet pulp, bacterial cellulose, Valonia algae, and tunicates.
  • Examples of commercially available nano-crystalline cellulose that may be used in the exemplary compositions and polymer foams described herein include BioPlus-LTM crystals from American Process, Inc. (Atlanta, Georgia) and Celluforce NCCTM nano-crystalline cellulose from Celluforce (Montreal, Canada).
  • the nano-crystalline cellulose is generally in the form of rod-like or whisker shaped particles with at least one dimension (e.g., length, width, diameter) less than 100 nm.
  • the nano-crystalline cellulose has an average particle diameter (or width) of 2 nm to 5 nm, including from 2.3 nm to 4.5 nm, and also including an average particle diameter (or width) of 4 nm to 5 nm.
  • the nano-crystalline cellulose has an average particle length of 40 nm to 500 nm, including from 40 nm to 400 nm, from 40 nm to 300 nm, from 40 nm to 200 nm, from 40 nm to 150 nm, and also including an average particle length of 40 nm to 115 nm.
  • the nano crystalline cellulose in the composition for forming a polymer foam has an average particle diameter (or width) of 2 nm to 5 nm and an average particle length of 40 nm to 115 nm.
  • the nano-crystalline cellulose in the exemplary compositions described herein may also be characterized by other properties including, but not limited to, crystallinity, bulk density, sulfur content, zeta potential, and crystallinity index.
  • the nano-crystalline cellulose has a crystallinity of 85% to 98%, including from 85% to 95%, and also including from 88% to 93%.
  • the nano-crystalline cellulose has a bulk density of 0.5 g/cm 3 to 1.5 g/cm 3 , including from 0.7 g/cm 3 to 1 5 g/cm 3 , and also including from 1 g/cm 3 to 1.5 g/cm 3 .
  • the nano-crystalline cellulose comprises 0.05% to 1% by weight sulfur, including from 0.05% to 0.9% by weight sulfur, from 0.05% to 0.1% by weight sulfur, and also including from 0.85% to 0.9% by weight sulfur.
  • the nano crystalline cellulose has a zeta potential of -25 mV to -40 mV, including from -25 mV to -30 mV, and also including from -30 mV to -40 mV.
  • the nano-crystalline cellulose has a crystallinity index of 40% to 80%, including from 40% to 70%, and also including from 40% to 65%.
  • the nano-crystalline cellulose in the composition for forming a polymer foam has an average particle diameter of 2 nm to 5 nm, an average particle length of 40 nm to 500 nm, and a zeta potential of -25 mV to -40 mV. In certain embodiments, the nano-crystalline cellulose in the composition for forming a polymer foam has an average particle diameter of 2 nm to 5 nm, an average particle length of 40 nm to 115 nm, and a zeta potential of -29.5 mV to -37 mV.
  • the nano-crystalline cellulose may be provided in the composition as part of a masterbatch.
  • the nano-crystalline cellulose may be extrusion compounded with a carrier polymer to form a nano-crystalline cellulose masterbatch.
  • the nano-crystalline cellulose comprises 5% to 25% by weight of the masterbatch (based on the total weight of the mastrbatch), including from 5% to 20%, from 5% to 15%, and also including from 5% to 10% by weight of the masterbatch.
  • the carrier polymer may be the same polymer used in the composition for forming the polymer foam, or may be a different polymer than the polymer used in the composition for forming the polymer foam.
  • the carrier polymer used to form the nano-crystalline cellulose masterbatch comprises polystyrene.
  • the carrier polymer used to form the nano-crystalline cellulose masterbatch consists of polystyrene.
  • the nano-crystalline cellulose when used in sufficient amounts, functions as an infrared attenuating agent in the polymer foam, which reduces the thermal conductivity of the polymer foam and, thus, increases the insulating capability of the polymer foam. Without wishing to be bound by theory, it is believed the infrared attenuating functionality results from the abundant number of C-OH bonds present in the nano-crystalline cellulose, which can absorb infrared radiation. It was also discovered that the nano-crystalline cellulose, when used in sufficient amounts, efficiently increases the water vapor permeability of the polymer foam, which makes the polymer foam more breathable.
  • the polymer foam When the polymer foam is used as a thermal insulation in or on the exterior of buildings, such breathability can reduce the risk of mold growth due moisture condensation and/or accumulation. Without wishing to be bound by theory, it is believed the hydrophilic nature of the nano-crystalline cellulose increases the water vapor permeability of the polymer foam.
  • the exemplary composition for forming a polymer foam comprises from 2% to 10% by weight nano-crystalline cellulose based on the total weight of the solids of the composition. In certain embodiments, the composition for forming a polymer foam comprises from 4% to 10% by weight nano-crystalline cellulose based on the total weight of the solids of the composition. In certain other embodiments, the composition for forming a polymer foam comprises from 4% to 8% by weight nano-crystalline cellulose based on the total weight of the solids of the composition.
  • the composition for forming a polymer foam comprises from 4% to 8% by weight nano crystalline cellulose based on the total weight of the solids of the composition, and the nano crystalline cellulose has an average particle diameter of 2 nm to 5 nm, an average particle length of 40 nm to 115 nm, and a zeta potential of -29.5 mV to -37 mV. It is contemplated that the nano-crystalline cellulose in the composition for forming the polymer foam may be characterized by any combination of the physical dimensions and other properties described above.
  • the exemplary composition for forming a polymer foam also includes a blowing agent.
  • a blowing agent any blowing agent suitable for making a polymer foam may be used in accordance with the present disclosure.
  • the composition for forming a polymer foam is free of chlorofluorocarbon (CFC) blowing agents.
  • CFC chlorofluorocarbon
  • the blowing agent may be selected based on the considerations of low global warming potential, low thermal conductivity, non-flammability, high solubility in polystyrene, high blowing power, low cost, and the overall safety of the blowing agent.
  • the blowing agents described herein may be used alone or in combination in the composition for forming the polymer foam.
  • the blowing agent comprises a hydrofluorocarbon
  • HFC hydrogen fluoroethane
  • HFC- 152a difluoroethane
  • HFC-152 difluoroethane
  • FIFC-l34a 1 , 1 , 1 ,2-tetrafluoroethane
  • HFC-134 l,l,2,2-tetrafluroethane
  • HFC-l43a difluoromethane
  • HFC-32 pentafluoroethane (HFC-125); fluoroethane (HFC-161); l,l,2,2,3,3-hexafluoropropane (HFC-236ca); l, l,l,2,3,3-hexafluoropropane (HFC-236
  • the blowing agent used in the composition comprises at least one of HFC-l34a, HFC-134, and HFC-152a.
  • the blowing agent used in the composition comprises HFC-134a, HFC-134, and HFC-l52a, wherein the amount of HFC-l34a comprises from 15% to 85% by weight of the blowing agent, the amount of HFC-134 comprises from 5% to 20% by weight of the blowing agent, and the amount of HFC-l52a comprises from 10% to 80% by weight of the blowing agent.
  • the blowing agent used in the composition comprises HFC-l34a, HFC-134, and HFC-l52a, wherein the amount of HFC-l34a comprises from 35% to 45% by weight of the blowing agent, the amount of HFC-134 comprises from 5% to 15% by weight of the blowing agent, and the amount of HFC-l52a comprises from 45% to 55% by weight of the blowing agent.
  • the blowing agent used in the composition comprises HFC-l34a, HFC-134, and HFC-l52a, wherein the amount of HFC-134a comprises 41% by weight of the blowing agent, the amount of HFC-134 comprises 9% by weight of the blowing agent, and the amount of HFC-l52a comprises 50% by weight of the blowing agent.
  • the blowing agent may comprise a hydrofluoroolefm
  • HFO trans-l-chloro-3,3,3- trifluoropropene
  • HFO-l243zf 3,3,3-trifluoropropene
  • 2,3,3- trifluoropropene 2,3,3- trifluoropropene
  • trans isomer 1,1, 3, 3-tetrafluoropropene; 2, 3, 3, 3-tetrafluoropropene (HFO-l234yf); (cis and/or trans)-l,2,3,3,3-pentafluoropropene (HFO-l225ye); l,l,3,3,3-pentafluoropropene (HFO-l225zc); l,
  • the blowing agent comprises HFO-l234ze.
  • the blowing agent used in the composition comprises an HFC and an HFO.
  • the blowing agent used in the composition comprises HFC-l52a and HFO-l234ze, wherein the amount of HFC-l52a comprises from 40% to 60% by weight of the blowing agent and the amount of HFO-1234ze comprises from 40% to 60% by weight of the blowing agent.
  • the blowing agent may be in the form of a liquid or gas (e.g ., a physical blowing agent) or may be generated in situ during production of the foam ⁇ e.g., a chemical blowing agent).
  • the blowing agent may be formed by decomposition of another constituent during production of the polymer foam.
  • a carbonate composition, polycarbonic acid, sodium bicarbonate, or azodicarbonamide and others that decompose and/or degrade to form nitrogen (N 2 ), carbon dioxide (C0 2 ), and water (H 2 0) upon heating may be added to the composition.
  • blowing agents useful in the practice of this disclosure include, but are not limited to, C2 to C9 aliphatic hydrocarbons (e.g., ethane, propane, n-butane, cyclopentane, isobutane, n-pentane, isopentane, and neopentane); Cl to C5 aliphatic alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, and butanol); atmospheric gases such as air, carbon dioxide (C0 2 ), nitrogen (N 2 ), and/or argon (Ar); water; ketones (e.g., acetone and methyl ethyl ketone); ethers (e.g., dimethyl ethers and diethyl ethers); methyl formate; acetone; and hydrogen peroxide.
  • C2 to C9 aliphatic hydrocarbons e.g., ethane, propane, n-but
  • the amount of blowing agent used in the exemplary composition for forming the polymer foam is generally from 1% to 15% by weight based upon the total weight of all ingredients in the composition excluding the blowing agent.
  • the blowing agent is present in an amount of 3% to 12% by weight, including from 5% to 10% by weight, and also including about 7 8% by weight based upon the total weight of all ingredients in the composition excluding the blowing agent.
  • the exemplary composition for forming a polymer foam may also contain one or more additives including, but not limited to, fire retarding agents, nucleating agents, plasticizing agents, pigments, elastomers, extrusion aids, antioxidants, fillers, antistatic agents, biocides, termiticides, colorants, oils, waxes, flame retardant synergists, infrared attenuating agents, and UY absorbers.
  • the additives may be included in the composition in amounts necessary to obtain desired characteristics of the composition during processing or the resulting polymer foam.
  • the composition for forming a polymer foam includes a fire retarding agent in an amount up to 5% by weight, including from 1% to 5% by weight based upon the total weight of all ingredients in the composition excluding the blowing agent.
  • Non-limiting examples of suitable fire retarding agents for use in the exemplary compositions described herein include brominated aliphatic compounds such as hexabromocyclododecane (HBCD) and pentabromocyclohexane, brominated phenyl ethers, esters of tetrabromophthalic acid, halogenated polymeric flame retardant such as brominated polymeric flame retardant based on styrene butadiene copolymers, phosphoric compounds, and combinations thereof.
  • brominated aliphatic compounds such as hexabromocyclododecane (HBCD) and pentabromocyclohexane
  • brominated phenyl ethers such as esters of tetrabromophthalic acid
  • halogenated polymeric flame retardant such as brominated polymeric flame retardant based on styrene butadiene copolymers, phosphoric compounds, and combinations thereof.
  • the composition for forming a polymer foam includes a nucleating agent in an amount up to 2% by weight, including from 0.2% to 2%, from 0.2% to 1%, and also including from 0.3% to 0.5% by weight based upon the total weight of all ingredients in the composition excluding the blowing agent.
  • suitable nucleating agents for use in the exemplary compositions described herein include talc, graphite, titanium dioxide, kaolin, and combinations thereof.
  • the exemplary polymer foam of the present disclosure may be made in a variety of ways.
  • the polymer foam is made using an extrusion process.
  • FIG. 1 illustrates a traditional extrusion apparatus 100 useful for making a polymer foam of the present disclosure.
  • the extrusion apparatus 100 may comprise a single or twin (not shown) screw extruder including a barrel 102 surrounding a screw 104 on which is provided a spiral flight 106 configured to compress, and thereby, heat material introduced into the screw extruder 100.
  • a polymer may be fed into the screw extruder 100 as a flowable solid, such as beads, granules or pellets, or as a liquid or semi liquid polymer melt, from one or more feed hoppers 108.
  • the decreasing spacing of the flight 106 defines a successively smaller space through which the polymer is forced by the rotation of the screw 104. This decreasing volume acts to increase the temperature of the polymer to obtain a polymer melt (if solid starting material was used) and/or to increase the temperature of the polymer melt.
  • one or more ports may be provided through the barrel 102 with associated apparatus 110 configured for injecting nano-crystalline cellulose (or nano-crystalline cellulose masterbatch) and/or one or more optional additives into the polymer to form a polymer melt.
  • one or more ports may be provided through the barrel 102 with associated apparatus 112 configured for injecting one or more blowing agents into the polymer melt to form a foamable mixture.
  • the nano-crystalline cellulose (or nano-crystalline cellulose masterbatch) is added into the feed hopper 108 along with the polymer. After the foamable mixture is formed, the foamable mixture may be subjected to additional blending in the screw extruder 100 sufficient to distribute each of the components generally uniformly throughout the foamable mixture.
  • the foamable mixture is then extruded through an extrusion die 114 and exits the die 114 into a region of reduced pressure (which may be above, or more typically below, atmospheric pressure), thereby allowing the blowing agent to expand and produce a polymer foam with cells that contain the expanded blowing agent.
  • the pressure reduction may be obtained gradually as the extruded foamable mixture advances through successively larger openings provided in the die 114 or through some suitable apparatus (not shown) provided downstream of the extrusion die 114 for controlling to some degree the manner in which the pressure applied to the foamable mixture is reduced.
  • the resulting polymer foam material may be subjected to additional processing such as calendaring, water immersion, cooling sprays, or other operations to control the thickness and other properties of the resulting polymer foam product.
  • the polymer foam formed from the exemplary compositions disclosed herein is a rigid, substantially closed cell, polymer foam board prepared by an extruding process.
  • extruded polymer foams generally have a cellular structure with cells defined by cell membranes and struts. Struts are formed at the intersection of the cell membranes, with the cell membranes covering interconnecting cellular windows between the stmts.
  • the average cell size of the polymer foam is from 0.05 mm (50 microns) to 0.4 mm (400 microns), including from 0.1 mm (100 microns) to 0.3 mm (300 microns), and also including from 0.11 mm (110 microns) to 0.25 mm (250 microns).
  • the phrase“substantially closed cell” is meant to indicate that the foam contains all closed cells or nearly all the cells in the cellular structure are closed.
  • no more than 5% of the cells are open cells, or otherwise“non-closed” cells.
  • from 0.01% to 5% of the cells of the polymer foam are open cells.
  • from 0.01% to 2% of the cells of the polymer foam are open cells.
  • from 0.4% to 1.25% of the cells of the polymer foam are open cells.
  • the polymer foam formed from the exemplary compositions disclosed herein have a density of less than 10 lb/ft 3 (pcf), or less than 5 pcf, or less than 3 pcf. In certain embodiments, the polymer foam has a density of 1.2 pcf to 4.5 pcf. In certain embodiments, the polymer foam has a density of 1.5 pcf to 2.5 pcf. In certain embodiments, the polymer foam has a density of 1.8 pcf to 2.1 pcf. In certain embodiments, the polymer foam has a density of 1.8 pcf to 2 pcf.
  • the polymer foam formed from the exemplary compositions disclosed herein possess a high level of dimensional stability.
  • the polymer foam formed from the exemplary compositions disclosed herein has a dimensional stability of 0% to 5% maximum dimensional change in any direction, at a temperature of 160 °F to 180 °F.
  • the polymer foams produced from the exemplary compositions disclosed herein which include from 2% by weight to 10% by weight nano-crystalline cellulose, were discovered to exhibit increased water vapor permeability and reduced thermal conductivity as compared to otherwise identical polymer foams that do not include nano-crystalline cellulose.
  • the polymer foam produced from the exemplary compositions disclosed herein has a water vapor permeability of 0.1 perm inch to 1.5 perm-inch, including from 1 perm inch to 1.5 perm-inch, from 1.1 perm inch to 1.5 perm inch, from 1.2 perm inch to 1.4 perm inch, and also including a water vapor permeability of 1.23 perm inch to 1.4 perm -inch.
  • Such water vapor permeability values provide for the enhanced breathability of the polymer foam, which can reduce the risk of mold growth due moisture condensation and/or accumulation, particularly when the polymer foam is used as a thermal insulation product for buildings.
  • the polymer foam produced from the exemplary compositions disclosed herein has a thermal conductivity of 0.154 BTU-in/(hr-ft 2 -°F) to 0.222 BTU-in/(hr-ft 2 -°F), including from 0.175 BTU-in/(hr-ft 2 -°F) to 0.220 BTU-in/(hr-ft 2 -°F), from 0.185 BTU-in/(hr-ft 2 -°F) to 0.210 BTU-in/(hr-ft 2 -°F), from 0.190 BTU-in/(hr-ft 2 -°F) to 0.205 BTU-in/(hr-ft 2 -°F), and also including from 0.195 BTU-in/(h
  • the polymer foam produced from the exemplary compositions disclosed herein has an R- value per inch of at least 4, including from 4 to 6.5, from 4.5 to 6.25, and also including from 5 to 6. In certain embodiments, the polymer foam produced from the exemplary compositions disclosed herein has an R-value per inch of about 5.
  • the polymer foam produced from the exemplary compositions disclosed herein may be formed into an insulation product such as a rigid insulation board, an insulation foam, a packaging product, and building insulation or underground insulation (for example, highway, airport runway, railway, and underground utility insulation).
  • an insulation product such as a rigid insulation board, an insulation foam, a packaging product, and building insulation or underground insulation (for example, highway, airport runway, railway, and underground utility insulation).
  • inventive concepts have been described above both genetically and with regard to various exemplary embodiments. Although the general inventive concepts have been set forth in what is believed to be exemplary illustrative embodiments, a variety of alternatives known to those of skill in the art can be selected within the generic disclosure. Additionally, the following examples are meant to better illustrate the inventive concepts, but are in no way intended to limit the general inventive concepts of the present disclosure.
  • XPS foams were prepared using a tandem extrusion system having a primary twin screw extruder and a secondary single screw extruder.
  • the resulting XPS foams were evaluated to determine various properties such as density (using ASTM D1622), average cell size (using ASTM D3576), open cell content (using ASTM D6226), thermal conductivity (using ASTM C518), and water vapor permeability (using ASTM E96).
  • the following raw materials were fed into the feed hopper at the front end of the primary extruder: polystyrene, nano-crystalline cellulose masterbatch, a flame retardant (e.g ., hexabromocyclododecane, polymeric brominated styrene butadiene), and talc (nucleating agent).
  • the blowing agent used to form the XPS foams was added into a separate port in the middle of the primary extruder and comprised a tertiary blend of HFC-l34a (about 41% by weight), HFC-134 (about 9% by weight), and HFC-l52a (about 50% by weight).
  • the primary extruder was used to melt and mix the various components fed into the primary extruder to create a homogeneous composition.
  • the melting and mixing process performed in the primary extruder was completed at about 200 °C and a pressure above 2,000 psi.
  • the homogeneous composition was then pushed from the exit of the primary extruder into the secondary extruder, where it was cooled from about 200 °C to the eventual foaming temperature of about 120 °C.
  • the rotation speed of the screw of the secondary extruder was much slower than the rotation speed of the screws of the primary extruder to ensure a long residence time for heat exchange and cooling. From the secondary extruder, the homogeneous composition flowed through a flat face foaming die where pressure was reduced to initiate foam cell nucleation and growth.
  • the foaming die temperature was about 110 °C to 130 °C and the foaming die pressure was about 600 psi to about 1500 psi.
  • the foamed polymer was compressed in a shaping die.
  • the resulting XPS foam board was trimmed and packaged.
  • the extrusion system was operated at a production rate of approximately 230 pounds per hour.
  • the XPS foam boards had a thickness of about 1 inch and an untrimmed width of about 24 inches.
  • Table 1 sets forth the components used to form the exemplary and comparative XPS foams, while Table 2 lists certain properties of the exemplary and comparative XPS foams.
  • the percentages listed in the column labeled “Feed Hopper Components” in Table 1 refer to the percent by weight of the total solids fed to the feed hopper.
  • the percentages listed in the column labeled“Port Component” in Table 1 refer to the percent by weight based upon the total weight of all components in the extruder excluding the blowing agent.
  • the nano-crystalline cellulose masterbatch was formed by extrusion compounding polystyrene (PS) with the nano-crystalline cellulose at 10% by weight of the total masterbatch.
  • PSD polystyrene
  • the nano-crystalline cellulose used in Control A and Examples 1-6 was BioPlus-LTM nano-crystalline cellulose (NCCA) from American Process, Inc. (Atlanta, Georgia), and the nano-crystalline cellulose used in Control B and Examples 7-12 was Celluforce NCCTM nano-crystalline cellulose (NCCB) from Celluforce (Montreal, Canada).
  • NCCA BioPlus-LTM nano-crystalline cellulose
  • NCCB Celluforce NCCTM nano-crystalline cellulose
  • Thermal conductivity values for Examples Comp. A and 1-6 are at 180 days aging.
  • Thermal conductivity values for Examples Comp. B and 7-12 are at 30 days aging.
  • the nano-crystalline cellulose incorporated into the XPS foam functions as an infrared attenuating agent, particularly at concentrations greater than 4% by weight, by reducing the thermal conductivity (k-value) of the XPS foam.
  • the use of nano crystalline cellulose at 8% by weight reduces the thermal conductivity of the XPS foam by about 0.003 BTU-in/(hr-ft-°F) to about 0.005 BTU-in/(hr-ft-°F).
  • the nano-crystalline cellulose incorporated into the XPS foam increases water vapor permeability, particularly at concentrations greater than 4% by weight.
  • the use of nano-crystalline cellulose at 8% by weight increases the water vapor permeability of the XPS foam by about 0.163 perm inch, or about 13.4%.
  • Such an increase in water vapor permeability would increase the breathability of the XPS foam, which can help avoid mold growth due to moisture condensation and/or accumulation.

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Abstract

La présente invention concerne une mousse polymère. La mousse polymère est formée à partir d'une composition qui comprend un polymère, de 2 % à 10 % en poids de cellulose nanocristalline par rapport au poids total de la mousse polymère, et au moins un agent d'expansion. La mousse polymère présente une conductivité thermique réduite (valeur k) et une perméabilité à la vapeur d'eau supérieure par comparaison à une mousse polymère autrement identique sans cellulose nanocristalline.
PCT/US2018/030108 2018-04-30 2018-04-30 Mousse polymère comprenant de la cellulose nanocristalline WO2019212460A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013003254A1 (fr) * 2011-06-27 2013-01-03 Owens Corning Intellectual Capital, Llc Agents d'atténuation infrarouge organiques
WO2014171430A1 (fr) * 2013-04-17 2014-10-23 ユニチカ株式会社 Mousse moulée
WO2014190428A1 (fr) * 2013-05-29 2014-12-04 Celluforce Inc. Composites à base de polyuréthane comprenant de la cellulose nanocristalline et procédé permettant d'améliorer les propriétés des polyuréthanes
WO2016132691A1 (fr) * 2015-02-16 2016-08-25 Dow Corning Toray Co., Ltd. Composition de caoutchouc de silicone apte à être formée en éponge et éponge en caoutchouc de silicone
WO2016150657A1 (fr) * 2015-03-24 2016-09-29 Sabic Global Technologies B.V. Matériau d'emballage comprenant une mousse de polyéthylène
US20170267827A1 (en) * 2016-03-21 2017-09-21 The Procter & Gamble Company High internal phase emulsion foam having cellulose nanoparticles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013003254A1 (fr) * 2011-06-27 2013-01-03 Owens Corning Intellectual Capital, Llc Agents d'atténuation infrarouge organiques
WO2014171430A1 (fr) * 2013-04-17 2014-10-23 ユニチカ株式会社 Mousse moulée
WO2014190428A1 (fr) * 2013-05-29 2014-12-04 Celluforce Inc. Composites à base de polyuréthane comprenant de la cellulose nanocristalline et procédé permettant d'améliorer les propriétés des polyuréthanes
WO2016132691A1 (fr) * 2015-02-16 2016-08-25 Dow Corning Toray Co., Ltd. Composition de caoutchouc de silicone apte à être formée en éponge et éponge en caoutchouc de silicone
WO2016150657A1 (fr) * 2015-03-24 2016-09-29 Sabic Global Technologies B.V. Matériau d'emballage comprenant une mousse de polyéthylène
US20170267827A1 (en) * 2016-03-21 2017-09-21 The Procter & Gamble Company High internal phase emulsion foam having cellulose nanoparticles

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