WO2019086966A1 - Fabrication de mousses polymères présentant des propriétés améliorées - Google Patents

Fabrication de mousses polymères présentant des propriétés améliorées Download PDF

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Publication number
WO2019086966A1
WO2019086966A1 PCT/IB2018/053545 IB2018053545W WO2019086966A1 WO 2019086966 A1 WO2019086966 A1 WO 2019086966A1 IB 2018053545 W IB2018053545 W IB 2018053545W WO 2019086966 A1 WO2019086966 A1 WO 2019086966A1
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Prior art keywords
temperature
pressure
mixture
granules
scf
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PCT/IB2018/053545
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English (en)
Inventor
Seyed Yaser DARYABARI
Mahsa HADIZADEH
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Daryabari Seyed Yaser
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Publication of WO2019086966A1 publication Critical patent/WO2019086966A1/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
    • C08J9/16—Making expandable particles
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B29C44/3453—Feeding the blowing agent to solid plastic material
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3461—Making or treating expandable particles
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/54—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length in the form of expandable particles or beads
    • 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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • 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
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • 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
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C08J9/008—Nanoparticles
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/08—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 chemical blowing agent developing carbon dioxide
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide

Definitions

  • the present disclosure generally relates to polymeric foams, and particularly, to a method for fabrication of microcellular polymeric foams with enhanced properties, particularly, with light microcellular polymeric foams with reduced shrinkage and warpage.
  • Polymeric foam is a suitable substitute for polymeric plastics due to less amount of raw plastic materials used for production of polymeric foams. Reducing the consumption of plastic materials leads to reduction of oil products, decreasing the cost of manufactured foam, and less damage to the environment is introduced.
  • Polymeric foams are a composite including gas bubbles dispersed within a plastic matrix, which make the final product weighed less than polymeric plastics with the same volume, which include a solid polymeric structure.
  • the polymeric foam should have a completely uniform microcellular structure to have the best mechanical properties, such as higher impact resistance, especially the least amount of shrinkage and warpage.
  • major changes are needed in the screw and nozzles of the regular plastic injection machines used for polymeric plastics production.
  • the cost of purchasing a plastic injection machine adapted for manufacturing polymeric foams is very high which is not possible for most industrial manufacturers except mega factories.
  • the present disclosure is directed to a method for fabrication of a polymeric foam.
  • the method may include forming a plurality of granules, forming a super critical fluid (SCF) from the plurality of granules by increasing temperature and pressure of the plurality of granules, and forming the polymeric foam from the SCF by decreasing temperature and pressure of the SCF.
  • Forming the plurality of granules may include forming a mixture including a polymer, a blowing agent, and an activator agent, and blending the mixture at a first temperature less than an activation temperature of the blowing agent.
  • Forming the SCF from the plurality of granules may be done by increasing temperature and pressure of the plurality of granules to a second temperature and a first pressure, where the second temperature may include a temperature more than the activation temperature of the blowing agent.
  • Forming the polymeric foam from the SCF may be done by decreasing temperature and pressure of the SCF to a third temperature and a second pressure.
  • blending the mixture at the first temperature may include feeding the mixture into an extruder, and blending the mixture within the extruder at the first temperature being less than the activation temperature of the blowing agent.
  • the extruder may include a twin-screw extruder.
  • forming the SCF from the plurality of granules by increasing temperature and pressure of the plurality of granules to the second temperature and the first pressure, and forming the polymeric foam from the SCF by decreasing temperature and pressure of the SCF to the third temperature and the second pressure may be done through an injection molding process.
  • the injection molding process may include inserting the plurality of granules into an injection molding apparatus, forming the SCF from the plurality of granules by increasing temperature and pressure of the plurality of granules within the injection molding apparatus to the second temperature and the first pressure, decreasing temperature and pressure of the SCF within the injection molding apparatus to the third temperature and the second pressure, and injecting the SCF with the third temperature and the second pressure from the injection molding apparatus into a mold.
  • the injection molding process may further include separating the polymeric foam from the mold.
  • decreasing the temperature and the pressure of the SCF within the injection molding apparatus to the third temperature and the second pressure, and injecting the SCF with the third temperature and the second pressure from the injection molding apparatus into the mold may be done concurrently.
  • forming the SCF from the plurality of granules by increasing temperature and pressure of the plurality of granules to the second temperature and the first pressure may include increasing the temperature of the plurality of granules to the second temperature being more than the activation temperature of the blowing agent, and increasing the pressure of the plurality of granules to the first pressure that may be between about 1 MPa and 100 MPa.
  • the polymer may include a thermoplastic polymer.
  • the mixture may include an amount of the polymer between about 95 % and about 99.5 % of weight of the mixture.
  • the mixture may include an amount of the activator agent between about 0.1 % and about 2.5 % of weight of the mixture.
  • the activator agent may include a plurality of zinc oxide (ZnO) nanoparticles.
  • the plurality of ZnO nanoparticles may include ZnO nanoparticles with a diameter of less than 50 nm.
  • the blowing agent may include at least one of Azodicarbonamide (ADC), Sodium hydrogen carbonate (NaHC0 3 ), and combinations thereof.
  • ADC Azodicarbonamide
  • NaHC0 3 Sodium hydrogen carbonate
  • the mixture may include an amount of the blowing agent between about 0.1 % and about 2.5 % of weight of the mixture
  • the mixture may further include a filler with an amount of between about 1 % and about 50 % of weight of the mixture. So, the mixture may include an amount of the polymer between about 50 % and about 98 % of weight of the mixture.
  • the filler may include at least one of wood powder, wood fibrous, wood particles, calcium carbonate (CaC0 3 ), talc, and combinations thereof.
  • the polymeric foam may include a plurality of bubbles with a size of less than 20 ⁇ .
  • FIG. 1 illustrates Differential Thermal Analysis (DTA) curves for ADC and high density polyethylene (HDPE), consistent with one or more exemplary embodiments of the present disclosure.
  • DTA Differential Thermal Analysis
  • FIG. 2 illustrates a schematic two dimensional view of a portion of a polymeric foam structure produced by a common injection molding process, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 3A illustrates an exemplary implementation of a method for fabrication of a polymeric foam, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 3B illustrates an exemplary implementation of a process for forming the plurality of granules, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 3C illustrates an exemplary implementation of an injection molding process for forming the SCF from the plurality of granules and forming the polymeric foam from the SCF, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 4 illustrates a Differential Thermal Analysis (DTA) of a mixture of ADC and ZnO nanoparticles in comparison with TPO (HDPE) as an exemplary polymer, consistent with one or more exemplary embodiments of the present disclosure.
  • DTA Differential Thermal Analysis
  • FIG. 5 illustrates a schematic view of a cross section of the die, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 6 illustrates a schematic two dimensional view of exemplary fabricated polymeric foam, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 7A illustrates a scanning electron microscopy (SEM) image of an exemplary uniform microcellular polymeric foam, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 7B illustrates a SEM image of an exemplary control polymeric foam, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 8 illustrates density reduction percent (%) of exemplary fabricated polymeric foams in comparison with a control non-foamed product for two injection volumes of about 85% and 90% at different amounts of wood particles, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 9 illustrates the impact resistance of the fabricated polymeric foams at an injection volume of about 90% in comparison with a control non-foamed product using different amounts of wood particles, consistent with one or more exemplary embodiments of the present disclosure.
  • FIG. 10 illustrates the cellular density (cells/m 3 ) of exemplary fabricated polymeric foams with different injection volumes of about 85%, about 90%, and about 95% using different amounts of wood particles, consistent with one or more exemplary embodiments of the present disclosure.
  • Blowing agents such as Azodicarbonamide (ADC) are used in polymerization process to produce polymeric foams.
  • ADC Azodicarbonamide
  • a "blowing agent” may refer to a substance which may be capable of producing a cellular structure via a foaming process in a variety of materials that may undergo hardening or phase transition, such as polymers, plastics, and metals. Blowing agents may be applied at temperatures above than an activation temperature of the blowing agents.
  • the cellular structure may be in a matrix that may reduce density, increase thermal and acoustic insulation, while increasing relative stiffness of the original polymer.
  • the blowing agent may also be called a foaming agent.
  • FIG. 1 shows a Differential Thermal Analysis (DTA) of ADC (curve 102) as an exemplary blowing agent and high density polyethylene (HDPE) (curve 104) as an exemplary polymer, consistent with one or more exemplary embodiments of the present disclosure.
  • DTA Differential Thermal Analysis
  • ADC ADC
  • HDPE high density polyethylene
  • FIG. 1 shows a Differential Thermal Analysis (DTA) of ADC (curve 102) as an exemplary blowing agent and high density polyethylene (HDPE) (curve 104) as an exemplary polymer, consistent with one or more exemplary embodiments of the present disclosure.
  • the activation temperature of ADC is about 205 °C and the melting temperature of HDPE is about 160 °C.
  • producing polymeric foams utilizing blowing agents by a common injection molding process may lead to fabrication of a foam structure without activating exemplary blowing agent; thereby, resulting in producing a polymeric foam structure with rare number of bubbles or pores non-uniformly dispersed within poly
  • FIG. 2 shows a schematic two dimensional image of a portion of a polymeric foam structure 200 which may be produced by a common injection molding process, consistent with one or more exemplary embodiments of the present disclosure. It may be observed that there is no dense microcellular structure within the produced foam which may not reach the desirable mechanically enhanced properties for the produced polymeric foam. Only a few number of bubbles 204 may be non-uniformly dispersed within polymeric matrix 202.
  • a method is disclosed to fabricate polymeric foams with a uniform microcellular structure and high mechanical resistance with minimum amount of shrinkage and warpage.
  • Exemplary method may utilize available devices for producing polymeric structures, such injection molding machines and extruders without any needs for complicated and costly devices and machines. Utilizing exemplary method may lead to decrease the consumption of polymer materials and increase the speed of production of polymeric foams and plastic injection products, which may bring a wide range of environmental benefits.
  • Exemplary method may include a two-step mixing processes that firstly, all raw materials on the basis of the same final formulation of the polymeric foam to be inserted into a plastic injection hopper may be mixed together at a high mixing rate, for example, by a co-rotating twin-screw extruder to form an intermediate granular structure at a temperature less than the activation temperature of an exemplary blowing agent within the raw materials.
  • the intermediate granular structure may be inserted to a plastic injection machine, for example, an injection molding apparatus to a second step mixing of the intermediate granular structure at a temperature above the activation temperature of exemplary blowing agent in order to activating exemplary blowing agent after the first step mixing; thereby, resulting in forming a uniform microcellular polymeric foam with minimal shrinkage and warpage.
  • a plastic injection machine for example, an injection molding apparatus to a second step mixing of the intermediate granular structure at a temperature above the activation temperature of exemplary blowing agent in order to activating exemplary blowing agent after the first step mixing; thereby, resulting in forming a uniform microcellular polymeric foam with minimal shrinkage and warpage.
  • FIG. 3A shows an exemplary implementation of method 300 for fabrication of a polymeric foam, consistent with one or more exemplary embodiments of the present disclosure.
  • Exemplary method 300 may include forming a plurality of granules (step 302), forming a super critical fluid (SCF) from the plurality of granules by increasing temperature and pressure of the plurality of granules (step 304), and Forming the polymeric foam from the super critical fluid (SCF) by decreasing temperature and pressure of the SCF (step 306).
  • step 302 forming a super critical fluid (SCF) from the plurality of granules by increasing temperature and pressure of the plurality of granules
  • SCF super critical fluid
  • Step 302 may include forming the plurality of granules.
  • FIG. 3B shows an exemplary implementation of a process for forming the plurality of granules (step 302), consistent with one or more exemplary embodiments of the present disclosure.
  • Forming the plurality of granules may include forming a mixture (step 310), and blending the mixture at a first temperature (step 312) in order to form the plurality of granules.
  • the mixture may include a polymer, a blowing agent, and an activator agent.
  • the first temperature may include a temperature less than an activation temperature of the blowing agent.
  • Step 310 may include forming the mixture that may include the polymer, the blowing agent, and the activator agent.
  • forming the mixture may include physically mixing of the polymer, the blowing agent, and the activator agent.
  • forming the mixture may include forming a first mixture by adding the activator agent to the blowing agent, and then, adding the polymer to the first mixture.
  • the polymer may include a thermoplastic polymer (TP), for example, a thermoplastic olefin (TPO).
  • TP thermoplastic polymer
  • TPO thermoplastic olefin
  • the polymer may include at least one of polyethylene (PE), polypropylene (PP), high density Polyethylene (HDPE), low density Polyethylene (LDPE), linear low density polyethylene (LLDPE), polyamide (PA), polystyrene (PS), acrylonitrile butadiene styrene (ABS), and combinations thereof.
  • the mixture may include an amount of the polymer between about 95 % and about 99.5 % of weight of the mixture.
  • the blowing agent may include at least one of Chloroflourocarbons (CFCs), Hydrochlorofluorocarbons (FCFCs), Hydrofluorocarbon (HFC), carbon dioxide (C0 2 ), Butane (C 4 Hio), Azodicarbonamide (ADC), Sodium hydrogen carbonate (NaHC0 3 ), and combinations thereof.
  • the blowing agent may include at least one of Azodicarbonamide (ADC), Sodium hydrogen carbonate (NaHC0 3 ), and combinations thereof.
  • the mixture may include an amount of the blowing agent between about 0.1 % and about 2.5 % of weight of the mixture.
  • the activator agent may include a nanostructured material, for example, a plurality of Zinc Oxide (ZnO) nanoparticles.
  • the plurality of ZnO nanoparticles may include ZnO nanoparticles with a diameter of less than about 100 nm.
  • the plurality of ZnO nanoparticles may include ZnO nanoparticles with a diameter of less than about 50 nm, for example, less than about 30 nm.
  • the mixture may include an amount of the activator agent between about 0.1 % and about 2.5 % of weight of the mixture.
  • the activator agent may be added to the blowing agent in the mixture to reduce the activation temperature of the blowing agent in order to provide activation of the blowing agent at a temperature of less than melting temperature of the polymer.
  • the polymeric foam may be fabricated with a dense amount of micrometer sized bubbles which may be uniformly distributed within the polymeric foam.
  • adding ZnO nanoparticles to ADC may act as a catalyst for activation of ADC; thereby, leading to reduce the activation temperature of ADC more than about 50 °C.
  • DTA Differential Thermal Analysis
  • ADC a mixture of ADC and ZnO nanoparticles
  • HDPE HDPE
  • the activation temperature of ADC may be reduced by adding the ZnO nanoparticles to ADC, so that the activation temperature of ADC may be more than melting temperature of the polymer by only about 5 degrees (°C).
  • the mixture may further include a filler with an amount of between about 1 % and about 50 % of weight of the mixture.
  • the mixture may include an amount of the polymer between about 50 % and about 98 % of weight of the mixture.
  • the filler may include at least one of wood powder, wood fibrous, wood particles, calcium carbonate (CaC0 3 ), talc, and combinations thereof.
  • forming the mixture may include mixing a first mixture with a second mixture, for example, by adding the first mixture to the second mixture.
  • the first mixture may include a mixture of the blowing agent and the activator agent
  • the second mixture may include the polymer and the filler.
  • forming the mixture may include forming the first mixture of the blowing agent and the activator agent, forming the second mixture of the polymer and the filler, and mixing the first mixture and the second mixture.
  • Step 312 may include blending the mixture at the first temperature, which may be less than the activation temperature of the blowing agent.
  • blending the mixture at the first temperature may include feeding the mixture into an extruder, and blending the mixture within the extruder at the first temperature less than the activation temperature of the blowing agent.
  • the blowing agent may include ADC and the activator agent may include ZnO nanoparticles, so that the first temperature may include a temperature between about 140 °C and about 160 °C which may be less than the activation temperature of ADC being about 205 °C.
  • the extruder may include a twin-screw extruder.
  • the extruder may include a co-rotating twin-screw extruder, or a counter-roating twin-screw extruder.
  • the mixture obtained from step 310 may be fed into an extruder, for example, through a hopper.
  • the mixture may be blended within the extruder at the first temperature, which may be less than the activation temperature of the blowing agent. All parts of the extruder may be maintained at the first temperature while the mixture in within the extruder.
  • the rotational speed of screws of the twin-screw extruder may be set at a speed of about 2 rpm or more.
  • the mixture may be blended within the extruder using a rotational speed between about 2 rpm and about 40 rpm.
  • a die for example, a cylindrical die may be installed at the end of the extruder which may be the external part, or the outlet of the extruder.
  • FIG. 5 shows a schematic view of a cross section 500 of the die, consistent with one or more exemplary embodiments of the present disclosure.
  • the die may include a plurality of openings 502, where a plurality of profiles (or strings) may be exited from the openings 502 after blending the mixture at the first temperature within the extruder.
  • Each opening of the plurality of openings 502 may have a diameter between about 1 mm and about 7 mm.
  • the temperature of the die may be maintained at the first temperature.
  • the plurality of granules may be obtained by cutting the plurality of profiles (or strings) into the plurality of granules with a length of about 5 mm.
  • the plurality of profiles exiting from the die may be cut or granulated to form the plurality of granules, for example, by cutting at a specific length.
  • the plurality of granules may be dried in an oven for further use.
  • each granule of the plurality of granules may include a rod shaped granule with a diameter of about 8 mm or less, and a length of about 10 mm or less.
  • each granule of the plurality of granules may include a rod shaped granule with a diameter between about 1 mm and about 7 mm, and a length of about 5 mm.
  • the plurality of granules may include a plurality of foamable granules that may be used in following steps of exemplary method 300 to form the polymeric foam.
  • Step 304 may include forming the super critical fluid (SCF) from the plurality of granules by increasing temperature and pressure of the plurality of granules to a second temperature and a first pressure.
  • the second temperature may include a temperature more than the activation temperature of the blowing agent.
  • the blowing agent may be activated at the second temperature; thereby, resulting in producing bubbles in the polymeric foam that may be formed in step 306.
  • forming the SCF from the plurality of granules by increasing temperature and pressure of the plurality of granules to the second temperature and the first pressure may include increasing the temperature of the plurality of granules to the second temperature more than the activation temperature of the blowing agent, and increasing the pressure of the plurality of granules to the first pressure between about 1 MPa and about 100 MPa.
  • the blowing agent may include ADC and the activator agent may include ZnO nanoparticles. So, the second temperature may include a temperature more than about 190 °C.
  • Step 306 may include forming the polymeric foam from the SCF by decreasing temperature and pressure of the SCF to a third temperature and a second pressure.
  • the third temperature may be between about 190 °C and about 280 °C.
  • the second pressure may be between about 1 MPa and about 100 MPa.
  • forming the SCF from the plurality of granules by increasing temperature and pressure of the plurality of granules to the second temperature and the first pressure (step 304), and forming the polymeric foam from the SCF by decreasing temperature and pressure of the SCF to the third temperature and the second pressure (step 306) may be done through an injection molding process.
  • FIG. 3C shows an exemplary implementation of an injection molding process 318 for forming the SCF from the plurality of granules and forming the polymeric foam from the SCF, consistent with one or more exemplary embodiments of the present disclosure.
  • Exemplary injection molding process 318 may include inserting the plurality of granules into an injection molding apparatus (step 320), forming the SCF from the plurality of granules by increasing temperature and pressure of the plurality of granules within the injection molding apparatus to the second temperature and the first pressure (step 322), decreasing temperature and pressure of the SCF within the injection molding apparatus to the third temperature and the second pressure (step 324), and injecting the SCF with the third temperature and the second pressure from the injection molding apparatus into a mold (step 326).
  • the polymeric foam may be formed in the mold and exemplary injection molding process 318 may further include separating the polymeric foam from the mold (step 328).
  • the injection molding apparatus may include an injection molding machine, which may be regularly used for plastics production.
  • FIG. 6 shows a schematic two dimensional view of exemplary fabricated polymeric foam, consistent with one or more exemplary embodiments of the present disclosure. It may be observed that using exemplary method 300, exemplary polymeric foam may have a uniform and dense microcellular structure of a plurality of micrometer sized bubbles 602 that may be dispersed uniformly within a polymeric matrix 604.
  • exemplary polymeric foam may include the plurality of bubbles 602 with a size of less than about 100 ⁇ .
  • exemplary polymeric foam may include the plurality of bubbles 602 with a size of less than about 20 ⁇ .
  • each bubble of include the plurality of bubbles 602 may have a size of about 5 ⁇ .
  • Exemplary polymeric foam may include the plurality of bubbles 602 with a cellular density of more than about 10 9 cells/m 3 of volume of the polymeric foam.
  • Exemplary polymeric foam may have lower density of a polymeric product, which may be fabricated from a thermoplastic polymr without using a blowing agent.
  • Exemplary polymeric foam may have a density about 20% lower than density of such polymeric product.
  • an exemplary polymeric foam was prepared using exemplary method 100 described above.
  • Polyethylene (PE) was used as a thermoplastic polymer with a high density of about 0.956 g/cm3 and high MFI of about 20 g/10 min. Wood particles of different types of woods were mixed together and were screened so that a wood powder with a particles size of less than 150 ⁇ was produced. The wood powder was dried at about 90 °C for about 72 hours.
  • Azodicarbonamide (ADC) was used as an exemplary blowing agent with an amount of about 50% of weight of a mixture including zinc oxide (ZnO) nanoparticles with a size of less than about 50 nm and with an amount of about 50% of weight of the mixture. The presence of ZnO nanoparticles resulted in reducing the activation temperature of ADC from about 210 °C to about 154 °C.
  • PE was mixed with paraffin oil (about 1% of the weight of the produce polymeric foam), then the obtained mixture was mixed with the mixture of ADC (about 0.5% of the weight of the produce polymeric foam) and ZnO (about 0.5% of the weight of the produce polymeric foam).
  • the obtained mixture of PE, paraffin oil, ADC, and ZnO was mixed with the dried wood powder to obtain a feed mixture.
  • the feed mixture was fed to a twin-screw extruder.
  • a cylindrical die with a diameter of about 15 mm and a length of about 150 mm was installed at the external part of exemplary twin-screw extruder to produce rod shaped profiles of wood- plastic composites (WPC).
  • the temperatures of all parts within the twin-screw extruder and the die temperature were maintained the same at about 145 °C.
  • the rotational speed of screws of the twin-screw extruder was set at about 6 rpm.
  • the produced rod shaped profiles with diameter of about 5 mm were cooled in the ambient temperature and grinded (granulated) to granules using a grinder. Then, the obtained granules were dried in an oven. Dried granules were fed into an injection molding machine and the polymeric foam was produced at an injection presser of about 70 MPa.
  • the produced molten polymeric foam was injected into a mold with a temperature of about 60 °C.
  • FIG. 7 A shows a scanning electron microscopy (SEM) image of an exemplary uniform microcellular polymeric foam produced according to the process described hereinabove, consistent with one or more exemplary embodiments of the present disclosure. It may be observed that there is a plurality of cells 702 with a size of about 50 ⁇ which are uniformly and densely dispersed within exemplary polymeric matrix 704.
  • SEM scanning electron microscopy
  • FIG. 7B shows a SEM image of exemplary control polymeric foam, consistent with one or more exemplary embodiments of the present disclosure. It may be observed that exemplary control polymeric foam may include a few large cells with a size of about 180 ⁇ which may not reach the desirable microcellular structure and characteristics for polymeric foams acceptable for different applications and industries.
  • EXAMPLE 2 mechanical analysis and characterization of the polymeric foams
  • FIG. 8 shows density reduction percent (%) of the fabricated polymeric foams in comparison with a control non-foamed product for two injection volumes of about 85% (curve 802) and 90% (curve 804) at different amounts of wood particles, consistent with one or more exemplary embodiments of the present disclosure.
  • injection volume may refer to a percentage of exemplary mold volume used in exemplary method 300 that may be filled with exemplary fabricated foam or generally, with an exemplary fabricated plastic produced by exemplary injection molding process.
  • more reduction in density and lighter polymeric foams may be obtained by applying an injection volume of about 85% in comparison with an injection volume of about 90%.
  • a 23% decrease in density may be obtained at injection volume of about 85% using about 40% of wood particles by weight of the fabricated polymeric foam.
  • Density reduction may be obtained with an amount of about 18%, 20%, 23%, and 16% using a weight percent of wood particles of about 20%, 30%, 40%, and 50% of the fabricated polymeric foam, respectively, which may be produced at injection volume of about 85%.
  • FIG. 9 shows the impact resistance of the fabricated polymeric foams at an injection volume of about 90% (curve 902) in comparison with a control non-foamed product (curve 904) using different amounts of wood particles, consistent with one or more exemplary embodiments of the present disclosure.
  • the results may show that by increasing the weight percentage of the wood particles in exemplary fabricated polymeric foams, the impact resistance of the products may be reduced, and in all groups the impact resistance of the foamed polymers may be more than non-foamed samples. This increase may be one of the most important benefits of foamed samples.
  • the cells in the foam structure due to their fineness may act as a barrier to crack growth during impact failure and increase the resistance of the foamed sample to the impact.
  • the impact resistance of exemplary fabricated polymeric foams at 90% injection volume with about 20 wt%, 30 wt%, 40 wt%, and 50 wt% of wood by weight of the polymeric foam may be improved by about 12%, 15%, 20% and 6%, respectively.
  • the size of the cells or bubbles within the microcellular structure of exemplary fabricated polymeric foams may be attributed to a 20% increase in the impact resistance of polymeric foam with about 40 wt% of wood particles.
  • other factors such as relative density, number and size of cells (bubbles) amy also affect the amount of impact resistance.
  • FIG. 10 shows the cellular density (cells/m 3 ) of exemplary fabricated polymeric foams with different injection volumes of about 85% (curve 1002), about 90% (curve 1004), and about 95% (curve 1006) using different amounts of wood particles, consistent with one or more exemplary embodiments of the present disclosure.
  • the samples with an structure of wood-plastic foam may be divided into two groups: the first group of samples with about 40 wt% of wood or less, and the second group of samples with higher amount of wood.
  • a method for producing a microcellular polymeric foam with a minimum amount of shrinkage and distortion which may have reinforced and highly improved mechanical properties.
  • Exemplary method may be utilized by common devices for producing polymers, for example, an extruder and an injection molding apparatus, to produce a polymeric foam with a uniform distributed plurality of bubbles or voids within a polymeric matrix.
  • Exemplary polymeric foam may be used in industrial and domestic applications.
  • Exemplary polymeric foam may have a high energy absorption capacity, which may be useful for shock applications, acoustic and thermal insulating applications.
  • Exemplary polymeric foam may be used in aircraft and automotive industry, buildings, and packaging applications.
  • Exemplary polymeric foam with combined enhanced mechanical properties and low density may also be used as structural materials.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une mousse polymère. L'invention comprend la formation d'une pluralité de granulés, la formation d'un fluide supercritique (SCF) à partir de la pluralité de granulés, par élévation de la température et de la pression de la pluralité de granulés, et la formation de la mousse polymère à partir du SCF, par abaissement de la température et de la pression du SCF. La formation de la pluralité de granulés comprend la formation d'un mélange comprenant un polymère, un agent porogène et un agent activateur, et le mélange du mélange à une première température inférieure à une température d'activation de l'agent porogène.
PCT/IB2018/053545 2017-11-01 2018-05-20 Fabrication de mousses polymères présentant des propriétés améliorées WO2019086966A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3321413A (en) * 1964-02-21 1967-05-23 Nat Polychemicals Inc Activated azodicarbonamide blowing agent compositions
US5158986A (en) * 1991-04-05 1992-10-27 Massachusetts Institute Of Technology Microcellular thermoplastic foamed with supercritical fluid
US20120061867A1 (en) * 2010-09-10 2012-03-15 Playtex Products Llc Polymer pellets containing supercritical fluid and methods of making and using
CN103102583B (zh) * 2011-11-11 2016-08-03 上海杰事杰新材料(集团)股份有限公司 一种聚丙烯微孔发泡材料及其制备方法
CN107283711A (zh) * 2017-07-12 2017-10-24 青岛中诚高分子科技有限公司 一种热塑性聚合物发泡珠粒成型体及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3321413A (en) * 1964-02-21 1967-05-23 Nat Polychemicals Inc Activated azodicarbonamide blowing agent compositions
US5158986A (en) * 1991-04-05 1992-10-27 Massachusetts Institute Of Technology Microcellular thermoplastic foamed with supercritical fluid
US20120061867A1 (en) * 2010-09-10 2012-03-15 Playtex Products Llc Polymer pellets containing supercritical fluid and methods of making and using
CN103102583B (zh) * 2011-11-11 2016-08-03 上海杰事杰新材料(集团)股份有限公司 一种聚丙烯微孔发泡材料及其制备方法
CN107283711A (zh) * 2017-07-12 2017-10-24 青岛中诚高分子科技有限公司 一种热塑性聚合物发泡珠粒成型体及其制备方法

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