EP2729521A2 - Mousses compostables ou d'origine biologique, et procédé de fabrication et d'utilisation - Google Patents

Mousses compostables ou d'origine biologique, et procédé de fabrication et d'utilisation

Info

Publication number
EP2729521A2
EP2729521A2 EP12807830.0A EP12807830A EP2729521A2 EP 2729521 A2 EP2729521 A2 EP 2729521A2 EP 12807830 A EP12807830 A EP 12807830A EP 2729521 A2 EP2729521 A2 EP 2729521A2
Authority
EP
European Patent Office
Prior art keywords
composition
blowing agent
foamed
polymer
compostable
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP12807830.0A
Other languages
German (de)
English (en)
Other versions
EP2729521A4 (fr
Inventor
Adam Pawloski
Jeffrey Cernohous
Kent Kaske
Garrett Van Gorden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lifoam Industries LLC
Original Assignee
Lifoam Industries 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
Priority claimed from US13/178,293 external-priority patent/US20120009420A1/en
Priority claimed from US13/178,272 external-priority patent/US20120010307A1/en
Priority claimed from US13/230,158 external-priority patent/US8962706B2/en
Application filed by Lifoam Industries LLC filed Critical Lifoam Industries LLC
Publication of EP2729521A2 publication Critical patent/EP2729521A2/fr
Publication of EP2729521A4 publication Critical patent/EP2729521A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B29C44/3469—Cell or pore nucleation
    • B29C44/348—Cell or pore nucleation by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased
    • 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
    • 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
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • This invention relates generally to compostable or biobased material compositions and to novel methods for producing lightweight, compostable or biobased foams and, in particular, to methods for producing foams using melt processing techniques to blend compostable or biobased materials and blowing agents that, in certain particularly preferred embodiments, do not contain any volatile organic components (VOCs) such as pentane.
  • VOCs volatile organic components
  • the compositions and processes are useful for the production of a variety of products.
  • Polymeric foams include a plurality of voids, also called cells, in a polymer matrix. By replacing solid plastic with voids, polymeric foams use fewer raw materials than solid plastics for a given volume. Thus, by using polymeric foams instead of solid plastics, material costs can be reduced in many applications. Additionally, foams are very good insulators that can seal building structures from air and moisture intrusion, save on utility bills, and add strength to the building.
  • Micro cellular foams have smaller cell sizes and higher cell densities than conventional polymeric foams.
  • Foam processes incorporate nucleating agents, some of which are inorganic solid particles, into the polymer melt during processing. These agents can be of a variety of compositions, such as talc and calcium carbonate, and are incorporated into the polymer melt typically to promote cell nucleation. The dispersion of nucleating agents within the polymer mixture is often times critical in forming a uniform cell structure.
  • the material used for expandable polystyrene is typically an amorphous polymer that exhibits a glass transition temperature of about 95° C and a melting temperature of about 240° C.
  • the process of converting EPS resins into expanded polystyrene foam articles requires three main stages: pre-expansion, maturation, and molding. Expandable beads produced from polystyrene and a blowing agent are made, and then expanded by steam in a pre-expander. The purpose of pre-expansion is to produce foam particles of the desired density for a specific application. During pre- expansion, the EPS beads are fed to a pre-expander vessel containing an agitator and controlled steam and air supplies.
  • the introduction of steam into the pre-expander yields two effects: the EPS beads soften and the blowing agent that is dispersed within the EPS beads, typically pentane, heats to a temperature above its boiling point. These two conditions cause the EPS beads to expand in volume. The diameter of the particles increases while the density of the resin decreases.
  • the density of pre-expanded granules is about 1000 kg/m 3 , and that of expanded beads lies in the range of 20 to 200 kg/m 3 ; depending on the process, a 5 to 50 times reduction in density may be achieved.
  • Maturation serves several purposes. It allows the vacuum that was created within the cells of the foam particles during pre-expansion to reach equilibrium with the surrounding atmospheric pressure. It permits residual moisture on the surface of the foam particles to evaporate. And, it provides for the dissipation of excess residual blowing agent. Maturation time depends on numerous factors, including blowing agent content of the original resin, pre-expanded density, and environmental factors. Pre- expanded beads that are not properly matured are sensitive to physical and thermal shock. Molding of such beads before maturation may cause the cells within the particles to rupture, thereby producing an undesirable molded foam part.
  • the pre-expanded beads are transferred to a molding machine containing one or more cavities that are shaped for the desired molded foam article(s).
  • the purpose of molding is to fuse the foam particles together into a single foam part.
  • Molding of EPS may follow a simple sequence: first, fill the mold cavity with pre-expanded beads; heat the mold by introducing steam; cool the molded foam article within the mold cavity; and eject the finished part from the mold cavity.
  • the steam that is introduced to the molding machine causes the beads to soften and expand even further, due to residual foaming agent, such as pentane or impregnated C0 2 .
  • residual foaming agent such as pentane or impregnated C0 2 .
  • a common approach to creating biodegradable products is to combine polylactic acid (PLA) with starch to create a hydrolytically degradable composition. Difficulties have been encountered in producing starch based polymers particularly by hot melt extrusion. The molecular structure of the starch is adversely affected by the shear stresses and temperature conditions needed to plasticize the starch and pass it through an extrusion die.
  • PLA polylactic acid
  • Blowing agents typically are introduced into polymeric material to make polymer foams in one of two ways.
  • a chemical blowing agent is mixed with the polymer.
  • the chemical blowing agent undergoes a chemical reaction in the polymeric material, typically under conditions in which the polymer is molten, causing formation of a gas.
  • Chemical blowing agents generally are low molecular weight organic compounds that decompose at a particular temperature and release a gas such as nitrogen, carbon dioxide, or carbon monoxide.
  • a physical blowing agent i.e., a fluid that is a gas under ambient conditions, is injected into a molten polymeric stream to form a mixture. The mixture is subjected to a pressure drop, causing the blowing agent to expand and form bubbles (cells) in the polymer.
  • U.S. Patent No. 6,593,384 to Anderson et al. describes expandable particles produced using broad polymer materials and a physical blowing agent.
  • U.S. Patent No. 7,226,615 to Yuksel et al. describes an expandable foam based on broad disclosure of biomaterials combined with a bicarbonate blowing agent.
  • U.S. Published Patent Application No. 2006/0167122 by Haraguchi et al. describes expandable particles derived from the combination of PLA, a blowing agent, and a polyolefin wax.
  • U.S. Published Patent Application No. 2010/0029793 by Witt et al. describes a method of producing PLA foam by impregnating resin beads with carbon dioxide (C0 2 ).
  • 4,473,665 to Martini-Vvedensky et al. describes a process for making a foamed polymer having cells less than about 100 microns in diameter.
  • a material precursor is saturated with a blowing agent, the material is placed under high pressure, and the pressure is rapidly dropped to nucleate the blowing agent and to allow the formation of cells. The material then is frozen rapidly to maintain a desired distribution of microcells.
  • U.S. Patent No. 5,158,986 to Cha et al. describes formation of microcellular polymeric material using a supercritical fluid as a blowing agent. Using a batch process, the patent describes various processes to create nucleation sites.
  • U.S. Patent No. 5,866,053 to Park et al. describes a continuous process for forming microcellular foam.
  • the pressure on a single -phase solution of blowing agent and polymer is rapidly dropped to nucleate the material.
  • the nucleation rate is high enough to form a microcellular structure in the final product.
  • WO 98/08667 by Burnham et al. provides methods and systems for producing microcellular material, and microcellular articles.
  • a fluid, single-phase solution of a precursor of foamed polymeric material and a blowing agent is continuously nucleated by dividing the stream into separate portions and separately nucleating each of the separate portions, then recombining the streams.
  • the recombined stream may be shaped into a desired form, for example by a shaping die.
  • blowing agent levels can lead to smaller cells (a generally desirable result in the field of microcellular foams)
  • higher blowing agent levels also can cause cell interconnection (which by definition increases cell size and can compromise structural and other material properties) and less-than-optimal surface properties (compromised surface properties at higher gas levels can result from the natural tendency of the blowing agent to diffuse out of the material).
  • the physical blowing agent in some preferred embodiments is super critical C0 2 .
  • the composition is polymer of polylactic acid. In some embodiments, the content of D-isomer in the polylactic acid polymer is less than 6%. In other embodiments, the content of D-isomer in the polylactic acid polymer is less than 2%.
  • the bead comprises a nucleating agent and additives to improve melt rheology and viscosity.
  • the additives are selected from the group consisting of antioxidants; light stabilizers; fibers; foaming additives; electrically conductive additives; antiblocking agents; antistatic agents; heat stabilizers; impact modifiers; biocides; compatibilizers; tackifiers; colorants; coupling agents; and pigments.
  • the foamed beads are produced from more than 50% compostable materials, preferably more than 80% compostable materials. In other embodiments, the foamed beads have a polymer composition greater than 50 wt% biobased, preferably greater than 80 wt% biobased.
  • the foamed beads have a substantially closed cell structure after pelletization of the extrudate at the face of an extrusion die.
  • the foamed beads have a spherical or nearly spherical shape and a diameter in the range of about 1 mm to about 10 mm, preferably about 2 mm to about 5 mm, and more preferably about 1mm to about 4 mm.
  • the foamed beads further have a density of less than 0.045 g/cm 3 and a cell size diameter in the range of 50 ⁇ to 150 ⁇ .
  • a related object of the present invention is to provide a method for producing compostable or biobased foams using blowing agents, and preferably that do not contain volatile organic components.
  • a further related object of the present invention is to provide a method for producing compostable or biobased foams using blowing agents that preferably do not contain pentane.
  • a further object of the invention is to provide a compostable or biobased, foamed bead that can be fabricated into a three-dimensional shape.
  • EPS expandable polystyrene
  • thermal insulation a composition and process for producing foamed beads from a compostable or biobased polymer and for using such beads in producing a variety of items.
  • lightweight beads are produced by melt processing a compostable or biobased polymer and a blowing agent.
  • the melt processable composition includes additional additives that improve the rheological characteristics of the compostable or biobased polymer, making it more amenable for producing lightweight, foamed beads.
  • the foamed beads of this invention can be further processed using conventional molding equipment to provide a lightweight, compostable or biobased, foamed article.
  • Articles of this invention have utility in applications where conventional expandable polystyrene (EPS) is utilized today, including those applications relating to protective packaging, sound dampening, and thermal insulation.
  • EPS expandable polystyrene
  • Polymer compositions are widely utilized in numerous applications, including automotive, home construction, electronic and consumer goods products.
  • the polymers may be composed of either biobased polymers or petroleum-based polymers. Compostable or biobased polymers are preferred to address environmental concerns associated with disposal of the materials once they are no longer useful for their intended purpose and minimizing the use of petroleum. However, the polymers must meet certain physical and chemical characteristics in order for them to be suitable for the intended application.
  • the polymer composition In expandable foams, the polymer composition must be able to be fabricated into a three dimensional shape that is lightweight and provides impact, sound, and thermal resistance or protection.
  • the invention described herein discloses compostable or biobased foams having attributes that are required to form products that posses these attributes.
  • Fig. 1 shows a general process schematic for foamed bead production by extrusion foaming process according to the present invention.
  • Fig. 2 shows a cross-section of a foamed bead produced by an exemplary process according to one embodiment of the present invention.
  • Fig. 3 shows a summary flow chart illustrating the process flow for producing foamed articles according to the present invention.
  • Biodegradability refers to a compound that is subject to enzymatic decomposition, such as by microorganisms, or a compound, portions of which are subject to enzymatic decomposition, such as by microorganisms.
  • a polymer such as polylactic acid can be degraded by hydrolysis to individual lactic acid molecules that are subject to enzymatic decomposition by a wide variety of microorganisms.
  • Microorganisms typically can consume carboxylic acid-containing oligomers with molecular weights of up to about 1000 daltons, and preferably up to about 600 daltons, depending on the chemical and physical characteristics of the oligomer.
  • Biodegradable Polymer means a polymeric material or resin that is capable of chemically degrading into lower molecular weight materials.
  • Biobased means materials that are composed, in whole or in significant part, of biological products or renewable agricultural materials including plant, animal, and marine materials. Biobased products are synthesized from biological sources and refers to ingredients that reduce the use of non-renewable resources by integrating renewable ingredients as a replacement for at least a portion of the materials in a product, for example, replacement of petroleum used in making EPS. Biobased ingredients can be used in many products without hindering their performance.
  • “Chain Extender” means a material that when melt processed with a polymer, increases the molecular weight by reactively coupling chain ends.
  • Compostable means capable of undergoing biological decomposition, such that the material is not visually distinguishable and breaks down into carbon dioxide, water, inorganic compounds, and biomass.
  • Composting is the biological process of breaking down organic waste into a useful substance by various microorganisms in the presence of oxygen.
  • Extrudate is the semisolid material that has been extruded by forcing the material through a die opening.
  • Melt Processable Composition means a formulation that is melt processed, typically at elevated temperatures, by means of a conventional polymer processing technique such as extrusion or injection molding as an example.
  • Melt Processing Techniques means extrusion, injection molding, blow molding, rotomolding, or batch mixing.
  • Nucleating agent means a material that is added to a polymer melt that provides sites for crystal formation. For example, a higher degree of crystallinity and more uniform crystalline structure may be obtained by adding a nucleating agent.
  • Plasticizer means a material that is compatible with a compostable or biobased polymer after melt processing. Addition of a plasticizer to a compostable or biobased polymer has the effect of lowering the modulus of the film composition.
  • the present invention is also directed toward a variety of products that are made of compostable or biobased materials.
  • the compostable or biobased materials can include either or both of an externally or an internally modified polymer composition, as those terms are described below.
  • the polymer in the present materials breaks down by composting.
  • the degradation characteristics of the polymer in the present materials depend in large part on the type of material being made with the polymer.
  • the polymer needs to have suitable degradation characteristics so that when processed and produced into a final material, the material does not undergo significant degradation until after the useful life of the material.
  • the polymer of the present materials is further characterized as being compostable within a time frame in which products made from the materials break down after use.
  • the materials of this invention degrade in a time period of a few weeks to a few years, whereas similar mass-produced, nondegradable products typically require decades to centuries to break down naturally.
  • the compostable material degrades in less than 180 days.
  • the present invention describes compostable or biobased foam beads that are useful for fabricating foamed articles.
  • the foams of this invention are produced using a compound comprising a compostable or biobased thermoplastic polymer and a blowing agent.
  • Such compostable thermoplastic polymer material may be used to replace expandable polystyrene (EPS) with a foamed bead produced from the compostable or biobased polymer resin in the construction of foamed articles.
  • EPS expandable polystyrene
  • Additives including plasticizers and chain extenders are optionally included in the compostable or biobased composition.
  • the polymer has greater than 50% biobased content, most preferably greater than 80% biobased.
  • foamed beads are produced by cutting extrudate at the face of the extrusion die.
  • the foamed bead is subsequently optionally cooled by contacting with water, water vapor, air, carbon dioxide, or nitrogen gas.
  • the bead continues to foam, thus forming a closed cell foam structure with a continuous surface skin, i.e. there is no open cell structure at the surface of the bead.
  • the resulting compostable or biobased, foamed bead has a density of less than 0.15 g/cm .
  • the compostable or biobased, foamed bead has a density of preferably less than 0.075 g/cm , and most preferably less than 0.05 g/cm 3 .
  • more than 50 wt% of the foam is produced from compostable materials, as determined by ASTM D6400.
  • more than 80 wt% of the foam is a compostable material.
  • greater than 95 wt% of the foam is a compostable material.
  • the compostable or biobased polymers of this invention are produced by melt processing compostable or biobased polymers with a blowing agent and, optionally, additives that modify the rheology of the compostable or biobased polymer, including chain extenders and plasticizers.
  • the compostable or biobased polymers may include those polymers generally recognized by one of ordinary skill in the art to decompose into compounds having lower molecular weights.
  • Non-limiting examples of compostable or biobased polymers suitable for practicing the present invention include polysaccharides, peptides, polyesters, polyamino acids, polyvinyl alcohol, polyamides, polyalkylene glycols, and copolymers thereof.
  • the compostable or biobased polymer is a polyester.
  • polyesters include polylactic acids, poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA) and random or stereoregular copolymers of L-lactic acid and D-lactic acid, and derivatives thereof.
  • Other non-limiting examples of polyesters include polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, polyethylene succinate, polybutylene succinate, polybutylene adipate, polymalic acid, polyglycolic acid, polysuccinate, polyoxalate, polybutylene diglycolate, and polydioxanone.
  • Preferred polymer resins for this invention include known compostable materials derived from biological sources (e.g. compostable biopolymer resins), but synthetic polymers capable of being composted may also be used.
  • the biopolymer polylactic acid (PLA) is the most preferred example due to its known compostability and its biobased origins from agricultural (e.g. corn) feedstocks. Both amorphous and semi- crystalline PLA polymers can be used.
  • Examples of compostable or biobased polymers include Ingeo 2002D and Ingeo 4060D grade plastics and Ingeo 805 ID grade foam from Nature Works, LLC, and Cereplast Compostable 5001.
  • a compostable or biobased polymer is meltprocessed with a blowing agent to produce a light weight foamed bead.
  • Blowing agents are materials that can be incorporated into the melt processable composition (e.g., the premix of the additives, polymeric matrix, and/or optional fillers, either in melt or solid form) to produce cells through the release of a gas at the appropriate time during processing.
  • the amount and types of blowing agents influence the density of the finished product by its cell structure. Any suitable blowing agent may be used to produce the foamed material.
  • blowing agents There are two major types of blowing agents: physical and chemical.
  • Physical blowing agents tend to be volatile liquids or compressed gases that change state during melt processing to form a cellular structure.
  • the physical blowing agent is carbon dioxide.
  • the physical blowing agent of carbon dioxide in its supercritical state is mixed with the polymer melt.
  • Chemical blowing agents tend to be solids that decompose (e.g., thermally, reaction with other products, and so forth) to form gaseous decomposition products. The gases produced are finely distributed in the melt processable composition to provide a cellular structure.
  • Chemical blowing agents can be divided into two major classifications: organic and inorganic.
  • Organic blowing agents are available in a wide range of different chemistries, physical forms and modification, such as, for example, azodicarbonamide.
  • Inorganic blowing agents tend to be more limited.
  • An inorganic blowing agent may include one or more carbonate salts such as Sodium, Calcium, Potassium, and/or Magnesium carbonate salts.
  • sodium bicarbonate is used because it is inexpensive and readily decomposes to form carbon dioxide gas.
  • Sodium bicarbonate gradually decomposes when heated above about 120° C, with significant decomposition occurring between approximately 150° C and 200° C. In general, the higher the temperature, the more quickly the sodium bicarbonate decomposes.
  • An acid such as citric acid, may also be included in the foaming additive, or added separately to the melt processable composition, to facilitate decomposition of the blowing agent.
  • Chemical blowing agents are usually supplied in powder form or pellet form. The specific choice of the blowing agent will be related to the cost, desired cell development and gas yield and the desired properties of the foamed material.
  • blowing agents include water, carbonate and/or bicarbonate salts and other carbon dioxide releasing materials, diazo compounds and other nitrogen producing materials, carbon dioxide, decomposing polymeric materials such as poly (t- butylmethacrylate) and polyacrylic acid, alkane and cycloalkane gases such as pentane and butane, inert gases such as nitrogen, and the like.
  • the blowing agent may be hydrophilic or hydrophobic.
  • the blowing agent may be a solid blowing agent.
  • the blowing agent may include one or more carbonate and/or bicarbonate salts such as sodium, potassium, calcium, and/or magnesium carbonate and/or bicarbonate salts.
  • the blowing agent may also include sodium carbonate and sodium bicarbonate, or, alternatively, sodium bicarbonate alone.
  • the blowing agent may be inorganic.
  • blowing agent composition may include only the blowing agent, a more typical situation is where the blowing agent includes a polymeric carrier that is used to carry or hold the blowing agent.
  • This blowing agent concentrate may be dispersed in the polymeric carrier for transport and/or handling purposes.
  • the polymeric carrier may also be used to hold or carry any of the other materials or additives that are desired to be added to the melt processable composition.
  • the foaming additive includes at least about 2.5 wt% of blowing agent, at least about 5 wt% of blowing agent, or, suitably, at least about 10 wt% of blowing agent.
  • the foaming additive may include about 10 to 60 wt% of blowing agent, about 15 to 50 wt% of blowing agent, or, suitably, about 20 to 45 wt% of blowing agent.
  • the foaming additive may include about 0.05 to 90 wt% of blowing agent, about 0.1 to 50 wt% of blowing agent, or about 1 to 26 wt% of blowing agent.
  • the blowng agent concentrate may also include a polymeric carrier or material that is used to hold the other additives to form a single additive.
  • the polymeric carrier or polymeric component may be any suitable polymeric material such as hydrocarbon or non-hydrocarbon polymers.
  • the polymeric carrier should be capable of being melted or melt processed at temperatures below the activation temperature of the blowing agent. In some instances, however, a polymeric component having a melting point above the activation temperature of the blowing agent may be used as long as it is processed quickly enough so that a suitable amount of active blowing agent remains.
  • the polymeric carrier has a melting point of no more than about 150° C, no more than about 125° C, no more than about 100° C, or, suitably, no more than about 80° C.
  • the blowing agent concentrate contains a compostable or biobased polymer.
  • a plasticizer may be added or incorporated into the composition to address desired physical characteristics of the melt processable composition.
  • plasticizers include polyalkylene glycols and functionalized naturally occurring oils.
  • polyalkylene glycols include polyethylene glycols sold under the Carbowax trade name (Dow Chemical Co., Midland, MI).
  • functionalized naturally occurring oils include malinated or epoxidized soybean, linseed, or sunflower oils, which are commercially available from Cargill Inc.
  • the compostable or biobased composition may include a chain extender to increase the molecular weight of the compostable or biobased polymer during melt processing. This also has the effect of increasing melt viscosity and strength, which can improve the foamability of the compostable or biobased polymer.
  • chain extenders useful in this invention include those marketed under the CESA- extend trade name from Clariant, and those marketed under the Johncryl trade name from BASF.
  • moldability can be improved by adding a nucleating agent.
  • a nucleating agent include inorganic powder such as talc, kaolin, mica, silica, calcium carbonate, barium sulfate, titanium oxide, aluminum oxide, clay, bentonite, and diatomaceous earth, and known chemical blowing agents such as azodicarbodiamide.
  • talc is preferred because it facilitates control of the cell diameter.
  • the content of the nucleating agent varies depending on the type of the nucleating agent and the intended cell diameter.
  • the compostable or biobased, melt processable composition may contain other additives.
  • additives include plasticizers, chain extenders, antioxidants, light stabilizers, fibers, blowing agents, foaming additives, antiblocking agents, heat stabilizers, impact modifiers, biocides, compatibilizers, tackifiers, colorants, coupling agents, antistatic agents, electrically conductive fillers, and pigments.
  • the additives may be incorporated into the melt processable composition in the form of powders, pellets, granules, or in any other extrudable form.
  • the amount and type of additives in the melt processable composition may vary depending upon the polymeric matrix and the desired physical properties of the finished composition. Those skilled in the art of melt processing are capable of selecting appropriate amounts and types of additives to match with a specific polymeric matrix in order to achieve desired physical properties of the finished material.
  • the amount of components in the melt processable, compostable or biobased foam composition may vary depending upon the intended end use application.
  • the compostable or biobased polymer may comprise from about 40 to about 99 percent by weight of the final composition.
  • the blowing agent may be included at a level of up to 20 percent by weight.
  • the compostable or biobased plasticizer may comprise from about 1 to 50 percent by weight of the final composition, preferably between 1 and 20 percent by weight of the final composition.
  • the chain extender may comprise about 0.1 to 10 percent by weight of the final composition, preferably about 0.1 to 0.5 percent by weight.
  • Nucleating agents (such as talc) can be included up to about 5% by weight, more preferably less than 1% by weight, most preferably 0.5% by weight.
  • the physical blowing agent such as supercritical C0 2
  • the physical blowing agent such as supercritical C0 2
  • the melt early in the extruder mixing process is combined with the melt early in the extruder mixing process.
  • the supercritical C0 2 expands to form the foamed beads.
  • the processes found in the prior art require the quenching of the PLA prior to cutting.
  • the processes of the prior art do not create a foamed bead at the extruder but beads that are subsequently foamed resulting in a physically different type of bead that needs to be coated in order to work in a molding application.
  • heating of the beads during a secondary expansion process allows for expansion of the material to lower density.
  • the foamed beads may optionally be pressurized with a gas that will allow for additional expansion of the bead in the molding operation for the desired end product.
  • the optional pressurization is used to make the internal pressure of the cells within the foam greater than the atmospheric pressure.
  • the fact that the foam has a closed cell structure allows the bead to maintain an internal pressure greater than atmospheric pressure after the impregnation step. When the beads are heated during molding, this internal pressure allows for further expansion of the foamed bead.
  • Such pressurization or impregnation of the foamed beads will typically be done with a gas such as air, C0 2 , N 2 , hydrocarbon, etc. Then, the beads are put into a mold to form a selected product.
  • the temperature profile of the extruder must be carefully controlled to allow for melting and mixing of the solids, reaction with the chain extension agent (optional), mixing with blowing agent, (for example supercritical C0 2 ), and cooling of the melt mixture prior to extrusion through the die.
  • the temperatures of the initial barrel sections allows for melting and mixing of the solids, including the dispersion of nucleating agent within the melt.
  • the optional chain extension agent reacts with the chain ends of the polymer, increasing branching and molecular weight, which increases viscosity of the melt and improves the melt strength of the plastic.
  • a melt seal Prior to injection of the blowing agent, a melt seal is created within the extruder by careful design of internal screw elements to prevent the flow of the blowing agent from exiting the feed throat.
  • the melt seal maintains pressure within the extruder allowing the blowing agent to remain soluble within the melted plastic.
  • mixing elements are used to mix the blowing agent with the melt. Soluble blowing agent within the melt plasticizes the melt dramatically, greatly reducing its viscosity.
  • the plasticization effect allows for the cooling of the melt to below the normal melting temperature of the compostable or biobased polymer in the final sections of the extruder. The cooling is necessary to increase the viscosity of the plasticized melt, allowing for retention of a closed cell structure during foaming at the die.
  • Nucleating agents serve as nucleation sites for blowing agent evolution during foaming.
  • the blowing agent dissolved in the plastic melt comes out of solution into the gas phase.
  • the volume occupied by the blowing agent increases dramatically, producing a foamed structure.
  • the blowing agent will evenly evolve from its soluble state within the melt to its gaseous form during depressurization, thus producing a fine cellular foam.
  • the foaming can be uneven, producing large voids or open cell structure where cell walls are fractured and interconnected. Large voids and open cell structure creates a harder, more brittle foam.
  • Very low density foams with closed cell structure can be described as spongy, having a good elastic recovery after significant compression.
  • the melt processable, compostable or biobased foam composition of the invention can be prepared by any of a variety of ways.
  • the compostable or biobased polymer, blowing agent, nucleating agent, and optional additives can be combined together by any of the blending means usually employed in the plastics industry, such as with a mixing extruder.
  • the materials may, for example, be used in the form of a powder, a pellet, or a granular product.
  • the mixing operation is most conveniently carried out at a temperature above the melting point or softening point of the polymer.
  • the resulting melt-blended mixture can be processed into foamed beads by cutting the extrudate mixture of polymer and blowing agent at the face of the extrusion die.
  • a bead is formed before complete expansion of the foam has occurred.
  • a foamed bead is formed from expansion of the extrudate by the blowing agent.
  • the foamed bead cools by the release of blowing agent, but subsequent cooling can be applied by contacting with water, water vapor, air, carbon dioxide, or nitrogen gas.
  • the resulting foamed beads can be molded into a three-dimensional part using conventional equipment utilized in molding expandable polystyrene.
  • the foamed beads contain residual blowing agent and can be post expanded in the molding process.
  • the foamed beads are pressurized with a gas, such as air or carbon dioxide, before molding to allow for expansion during molding.
  • melt processing typically is performed at a temperature from about 80° to 300° C, although optimum operating temperatures are selected depending upon the melting point, melt viscosity, and thermal stability of the composition.
  • Different types of melt processing equipment such as extruders, may be used to process the melt processable compositions of this invention.
  • Extruders suitable for use with the present invention are described, for example, by Rauwendaal, C, "Polymer Extrusion,” Hansen Publishers, p. 11 - 33, 2001.
  • the resulting compostable or biobased, foamed bead has a specific gravity less than 0.15 g/cm . In another embodiment, the compostable or biobased, foamed bead has a specific gravity of preferably less than 0.075 g/cm , and most preferably less than 0.05 g/cm .
  • the polymer for making the foamed bead is greater than 50% biobased content, most preferably greater than 80 wt% biobased.
  • more than 50 wt% of the foam is compostable, as determined by ASTM D6400.
  • more than 80 wt% of the foam is compostable.
  • greater than 95 wt% of the foam is compostable.
  • the first three examples below utilize a single type of PLA resin. It is known, however, that the degree of crystallinity in PLA is controlled by two general aspects, first composition, and second by process.
  • the PLA polymer is composed of lactic acid monomers, but there are two types of lactic acid monomers. Although composed of the same elements, functional groups, and chemical bonds, the stereochemistry of the monomers is different.
  • the two isomers of lactic acid, the so-called 1 and d-isomers have a different three-dimensional 'handedness.' The result is that the type of isomer can affect the position of the pendant methyl groups along the backbone of the PLA polymer chain.
  • PLA chains that are 100% composed of either 1 or d-isomers will be highly crystalline because the polymer chains can pack tightly against each other. By introducing small concentrations of the other isomer, the crystallinity begins to decrease because the position of the pendant methyl groups begins to disrupt the higher order structure of crystallinity.
  • PLA with nearly 50/50 mixtures of 1 and d-isomers results in a completely amorphous polymer.
  • the 1-isomer of lactic acid is the predominant natural form of lactic acid, so most semi-crystalline PLAs are predominantly composed of 1- isomer with random impurities of the d-isomer.
  • the 805 ID resin has a d-isomer content of about 3.7 to 4.6%, whereas the 4032D resin has a d-isomer content less than 2% (between 1.2 and 1.6%).
  • a second aspect of thermal stability in PLA is the process and thermal history of the plastic.
  • PLA is slow to crystallize. Although the d-isomer content may be within an appropriate range to support crystallinity, this does not necessarily happen if the material is cooled too quickly. All crystallinity is lost when the plastic is heated above its melting point, and a slow thermal annealing is required to induce crystallization. Fillers, such as high performance talcs are often used to promote a more rapid crystallization, yet most extrusion applications that are hoping to take advantage of high crystallinity for thermal stability will require an annealing step between 100° and 130° C, to sufficiently crystallize the PLA.
  • FIG 1 shows a process schematic for bead production by an extrusion foaming process.
  • the extruder used for the mixing process in the examples below was a Leistritz ZSE 27 MAXX co-rotating twin-screw extruder having ten stages in the barrel.
  • the barrel of the extruder was equipped with an injection port to supply supercritical carbon dioxide (C0 2 ) into the plastic melt in the fourth barrel section.
  • C0 2 in the supercritical state was produced by pressurizing liquid C0 2 from a pressurized cylinder with a TharSFC P-50 high-pressure pump to a pressure of 27.6 MPa (4000 psi). All pressurized tubing was jacketed for cooling with an ethylene glycol - water mixture at a set point of 2° C (35° F).
  • an improvement on the production of lightweight foamed beads is described.
  • both a physical blowing agent and a chemical blowing agent are combined during the extrusion processes for the production of lightweight foamed beads.
  • the physical blowing agent preferably supercritical C0 2
  • the secondary blowing agent may be incorporated in one of three ways. In the first case, the secondary blowing agent may be incorporated upstream of the primary blowing agent. In the second case, the secondary blowing agent may be incorporated downstream of the primary blowing agent. And, in the third case, the secondary blowing agent may be incorporated simultaneously with the primary blowing agent. Preferably, for all cases, the primary blowing agent is a physical blowing agent like supercritical C0 2 . This primary blowing agent is used to provide the majority of the expansion during extrusion to produce the foamed beads.
  • the objective of the secondary blowing agent is to remain largely dormant during the extrusion and foamed bead formation so that it can be triggered during subsequent processing of the foamed bead in order to enable further expansion of the bead.
  • the process of the present invention is carefully designed so that the secondary blowing agent is not completely consumed during the extrusion foaming process.
  • the process of the present invention allows the secondary blowing agent to remain largely intact through the extrusion foam process, allowing the secondary blowing agent to be incorporated into the foamed bead.
  • chemical blowing agents are most appropriate for use as the secondary blowing agent.
  • the chemical blowing agent is added into the polymer melt of the extruder before or after the primary blowing agent is injected into the melt. Due to the elevated temperatures of the melt, it is possible that the chemical blowing agent will begin to decompose and contribute gas that can foam the polymer.
  • the extent of decomposition of the blowing agent can be controlled. Some decomposition may occur to release gas, but as long as some of the blowing agent remains in the extrudate, the foamed beads will contain it.
  • the secondary blowing agent is mixed with the primary blowing agent and injected into the polymer melt simultaneously.
  • supercritical C0 2 is the primary blowing agent and a chemical blowing agent is used as the secondary blowing agent.
  • the chemical blowing agent can be a liquid or a solid.
  • supercritical C02 may be used as a carrier phase to dissolve the chemical blowing agent to form a mixture.
  • the mixture is then injected into the barrel of the extruder to mix with the polymer melt.
  • the secondary blowing agent concentration is present in the range from about 0.5 to about 5 wt% in the foamed bead.
  • a dry mix blend of plastics was produced consisting of approximately 97% by weight of Nature Works Ingeo 805 ID polylactic acid (PLA), approximately 2% by weight of Clariant CESA-extend OMAN698498 styrene-acrylic multifunctional oligomeric reactant, and approximately 1% by weight of Cereplast ECA-023 talc masterbatch.
  • the dry mix of pellets was fed gravimetrically into the feed throat section of the twin-screw extruder.
  • the feed rate for the solids was set to 3.5 kg/hr (7.7 lbs/hr), and the screws were rotating at 40 rpm.
  • Supercritical carbon dioxide (C0 2 ) was injected into the plastic melt in the fourth barrel section at 10 g/min.
  • a single strand die with a 3 mm opening was bolted to the end of the extruder.
  • the melt pressure at the die was 1 1.7 MPa (1700 psi).
  • the extrudate was foamed to a density less than 0.04 g/cm 3 (2.5 lb/ft 3 ) with a closed cell structure.
  • the surface temperature of the strand extrudate was less than 40° C.
  • Example #1 The process described in Example #1 was followed and improved to include a pelletizing operation at the die face.
  • An off-axis, two-blade pelletizer was mounted to the extruder and die assembly. Foamed beads were cut at the face of the die with a pelletizer operating at 1500 rpm. The foamed beads were free flowing and did not stick together.
  • the surface of the foamed beads was complete and did not exhibit open or broken cells.
  • the density of the foamed beads was less than 0.04 g/cm (2.5 lb/ft 3 ), and the bead diameter was approximately 10 mm.
  • Example #1 The process described in Example #1 was modified to replace the 3 mm single strand die, with an eight-hole die having 0.8 mm die openings.
  • the new die included an adapter section that added one heating zone before the die.
  • the pelletizing system was changed to an on-axis, two-blade cutting system, operating at 2500 rpm.
  • the feed rate of the dry blend of resin, chain extender, and talc masterbatch was decreased to 2.3 kg/hr (5 lbs/hr).
  • the final process temperature profile during production of low density foam was adjusted to 210° C, 199° C, 177° C, 155° C, 115° C, 115° C, 115° C, 115° C, 115° C, 130° C, and 135° C across the extruder and die.
  • the extruder screws operated at 25 rpm.
  • the feed rate of supercritical C0 2 was 7.0 g/min at a pressure of about 10.3 MPa (1500 psi).
  • the melt pressure during operation of the extruder was about 15.8 MPa (2300 psi) behind the die.
  • the foamed beads produced had a diameter in the range of 2 mm to 5 mm with a density less than 0.045 g/cm 3 (2.8 lb/ft 3 ).
  • Figure 2 displays a micrograph taken by scanning electro-microscopy of a wedge-shaped cross-section of a foamed bead, showing a closed cell structure with cell size in the range of 50 to 150 ⁇ .
  • Example #3 The process described in Example #3 was modified to produce foamed beads with a smaller bead diameter and from a different composition.
  • the die was replaced with a twelve-hole die having 0.6 mm die openings.
  • the feed composition was pre- compounded on a 38 mm SHJ-38 co-rotating twin-screw extruder from Lantai Plastics Machinery Company with a flat temperature profile of 180° C.
  • a dry blend mix was prepared from approximately 87% by weight NatureWorks Ingeo 805 ID PLA, approximately 10% by weight of NatureWorks Ingeo 4032D PLA, approximately 2% by weight of Clariant CESA-extend OMAN698498 styrene-acrylic multifunctional oligomeric reactant, and approximately 1% by weight of Cereplast ECA-023 talc masterbatch.
  • the compounded formulation was subsequently fed into the feed throat of the Leistritz ZSE 27 MAXX extruder at 2.3 kg/hr (5.0 lbs/hr) with a screw speed of 25 rpm.
  • the feed rate of supercritical C0 2 was 7 g/min, and the temperature profile followed 210° C, 199° C, 177° C, 155° C, 115° C, 115° C, 1 15° C, 1 15° C, 115° C, 150° C, and 150° C.
  • the pelletizer operated at 1920 rpm, cutting the extrudate at the face of the extrusion die.
  • the melt pressure behind the die was about 15.2 MPa (2200 psi).
  • the foamed beads produced had a diameter in the range of 1 mm to 4 mm with a density less than 0.045 g/cm 3 (2.8 lb/ft 3 ) .
  • the foamed beads produced in this process were compared for relative heat stability to the foamed beads produced in Example #3. Placed side-by- side on a hot plate and heated with an increasing temperature ramp, the foamed beads softened at a higher temperature than the foamed beads from Example #3.
  • the foamed beads from Example #4 were pressurized in a sealed vessel at 0.45 MPa (65 psi) for less than 30 minutes. A rapid depressurization of the vessel was performed to remove the beads. The surface of the beads was taut from the internal pressure exceeding atmospheric pressure. The beads were vacuum fed into the cavity of a steam chest molding press (Hirsch HS 1400 D) within 1 minute of removal from the pressure vessel. The initial mold cavity temperature during fill was about 25° C. A conventional aluminum mold for expandable polystyrene (EPS) was used in the shape of a box. A four-step process was used for molding of a final product. The purge cycle was set for 1 second at 0.55 bar steam pressure and a 30% valve opening.
  • EPS expandable polystyrene
  • the first cross steam process was set for 20 seconds at 0.55 bar steam pressure and a 90% valve opening.
  • a second cross steam process reversing the direction of steam flow, was used for 20 seconds at a steam pressure of 0.65 bar and a 90% valve opening. Cooling water was applied for 15 seconds on both sides of the mold, followed by 30 seconds of cooling air at 4 bar pressure. After cooling air, 5 seconds of vacuum was applied.
  • the molded box was removed from the press. The shapes of the beads after molding clearly demonstrated secondary expansion of the foamed beads within the mold. Surface depressions and textures from the mold cavity were replicated into the surface of the article. Based on weight and geometry of the box, the density of the molded article was less than 0.03 g/cm 3 (2.0 lb/ft 3 ).
  • FIG. 3 shows a summary of the steps for creating a finished article using the composition and process described in the above examples.
  • the raw materials of PLA polymers, nucleating agent, and other additives are compounded.
  • the raw materials may be compounded in a separate extruder.
  • a blowing agent preferably supercritical C0 2
  • Small, lightweight, foamed beads are produced by hot face pelletization of extruded foamed strands at the extruder die face.
  • the foamed beads may be cooled using a water bath or other appropriate method.
  • the foamed beads are then pressurized to promote secondary expansion in the molder for the desired end product.
  • Such pressurization of the foamed beads will typically be done with a gas such as air, C0 2 , N 2 , hydrocarbon, etc.
  • the beads are put into a mold to form a selected product.
  • a steam press may be used for molding.
  • the beads are expanded in the mold to create a finished product.
  • the physical blowing agent such as supercritical C0 2
  • the physical blowing agent is combined with the melt early in the extruder mixing process.
  • the chemical blowing agent is added after the physical blowing agent, and in a relatively cooler portion of the extruder.
  • the chemical blowing agent is added before the physical blowing agent, again in a relatively cooler portion of the extruder. Then, as the mixture exits the extruder and is cut, the supercritical C0 2 expands to form the initial beads. Unlike the processes in the prior art, the admixture need not be quenched before the being cut or prevented from expanding as it exits the extruder. These beads have the chemical blowing agent already impregnated in them during the extrusion process.
  • the process is carefully controlled so that the secondary blowing agent is not completely consumed during the extrusion foaming process. Due to the low temperature used in the extrusion process at the point of addition of the chemical blowing agent, it can remain dormant during the extrusion process. Subsequently, heating of the beads during a secondary expansion process will liberate gases by thermal decomposition of the chemical blowing agent and thus, when combined with the right temperature for softening the plastic, allow for expansion of the material to lower density. During molding, for example, the beads are heated so they will melt together and the chemical blowing agent is activated causing a secondary expansion. That is, the thermal degradation of the blowing agent could be triggered during molding to enable fusion of the beads or a traditional pre-expansion operation to further lower density.
  • the chemical blowing agent is incorporated into the extrusion process downstream of the injection and mixing of the physical blowing agent.
  • the secondary blowing agent can be incorporated in the melt upstream of the injection and mixing of the physical blowing agent or simultaneously with the physical blowing agent.
  • the materials may be used in the form, for example, of a powder, a pellet, or a granular product.
  • the mixing operation is most conveniently carried out at a temperature above the melting point or softening point of the polymer.
  • the resulting melt-blended mixture can be processed into lightweight strands and subsequently cut into beads using a strand pelletizer.
  • foamed beads are produced by cutting the foamed strand at the face of the extrusion die. By cutting the extrudate at the face of the extrusion die, a bead is formed before complete expansion of the foam has occurred.
  • a foamed bead is formed from expansion of the extrudate by the physical blowing agent.
  • the foamed bead cools by the release of blowing agent, but subsequent cooling can be applied by contacting with water, water vapor, air, carbon dioxide, or nitrogen gas.
  • the resulting beads can be molded into a three-dimensional part using conventional equipment utilized in molding expandable polystyrene.
  • the objective of the secondary blowing agent is to remain largely dormant so that it can be triggered during subsequent processing of the foamed bead to enable further expansion of the bead.
  • the foamed beads contain residual chemical blowing agent and can be post expanded in the molding process.
  • more than 50 wt% of the foam contains materials that are compostable, as determined by ASTM D6400. In a preferred embodiment, more than 80 wt% of the foam contains materials that are compostable. In a most preferred embodiment, greater than 95 wt% of the foam contains materials that are compostable.
  • the expandable beads of one aspect of the present invention are produced using a compound comprising a compostable or biobased polyester and a blowing agent. Additives including plasticizers and chain extenders are optionally included in the compostable or biobased composition. Expandable beads can be produced using conventional melt processing techniques, such as single and twin-screw extrusion processes.
  • the compostable or biobased polymer is mixed with a hydrophobic additive by melt processing to produce pellets. These pellets are then impregnated with a blowing agent to make expandable beads. The expandable beads are then heated to cause foaming, producing foamed beads. The foamed beads are then molded into articles.
  • melt processing is used to mix compostable or biobased polymer, hydrophobic additive, and blowing agent to produce expandable beads directly from the melt processing operation.
  • extrudate from the die must be cooled rapidly to lock in the blowing agent so that it does not escape and foaming does not occur.
  • foaming occurs at a controlled time in a pre- expander operation by heating the expandable beads to produce foamed beads.
  • the foamed beads are then molded.
  • the resulting foamed bead has a density of less than 0.15 g/cm 3 . More preferably, the foamed bead has a density of less than 0.075 g/cm 3 , and most preferably less than 0.05 g/cm3.
  • more than 50 wt% of the foam is compostable, as determined by ASTM D6400. More preferably, more than 80% of the foam is compostable. In a most preferred embodiment, greater than 95% of the foam is compostable.
  • the plastic formulation of interest may be compounded, as required, into a homogeneous material for extrusion.
  • the plastic will be pelletized and optionally ground and classified into particles of a predetermined size, for example 0.25 mm diameter.
  • the polymer pellets may then be added into a stirred pressure tank with water to produce a slurry.
  • Solution stabilizers such as surfactants or salts, may be added to inhibit coagulation of pellets and to promote diffusion of hydrocarbon blowing agent into the polymer particles.
  • hydrocarbon blowing agent will be added to the slurry as a liquid.
  • the amount of hydrocarbon blowing agent added to the system will be predetermined based on the desired degree of hydrocarbon blowing agent in the expandable beads.
  • the pressure tank may be temperature controlled, for example by a circulating hot water bath. In some embodiments, the pressure tank will be mechanically sealed and pressurized using compressed gas, such as nitrogen.
  • a key aspect of on embodiment of the present invention is the ability to incorporate sufficient amounts of hydrocarbon blowing agent, when used, into the matrix of the compostable or biobased polymer such as PLA.
  • PLA does not exhibit the affinity for absorption of pentane that polystyrene exhibits to produce EPS. At room temperature, pentane readily absorbs into solid polystyrene, but this does not occur with PLA. It is therefore necessary to produce a composition of compostable or biobased polymer that allows for the impregnation of hydrocarbon blowing agent. To do this, amphiphilic or hydrophobic additives are added to the formulation, although not all amphiphilic or hydrophobic additives are favorable.
  • Amphiphilic or hydrophobic additives with low hydrophilic-lipophilic balance (HLB) numbers are preferred.
  • Block copolymer nonionic emulsifiers can also be used as hydrophobic additives to improve hydrocarbon blowing agent solubility.
  • Biologically derived oils such as soybean oil or acetylated monoglyceride derived from hydrogenated castor oil, can additionally be used to aid in hydrocarbon blowing agent solubility.
  • composition of the compostable or biobased polymer formulation may be additionally modified by the use of conventional plasticizers, chain extension agents, cross-linkers, and blends with other thermoplastics to improve other aspects of the processability and foaming capabilities of the resin.
  • the material compositions listed in Table 1 below were produced using melt processing by twin-screw extrusion.
  • NatureWorks 2002D polylactic acid (PLA) was the main component of all formulations. Additional raw materials included citric acid ester (Citroflex A-2, Vertellus Performance Materials), copolyester elastomer (Neostar FN007, Eastman Chemical), stearic acid surface treated calcium carbonate (Omyacarb FT, Omya North America), sorbitane monostearate (Span 60, Sigma-Aldrich), polyethylene glycol (Carbowax 8000, Dow Chemical), acetylated monoglyceride derived from hydrogenated castor oil Grindsted (Soft-N-Safe, Danisco), dicumyl peroxide (Sigma-Aldrich), ethoxylated nonionic emulsifier (Unithox 450, Baker Petrolite) and a custom maleated PLA.
  • the maleated PLA was
  • the pellets were removed, blotted dry to remove any surface coating of liquid pentane, and weighed.
  • the mass of pentane impregnated into the pellets was calculated by the difference in final and initial mass, and is expressed as a percentage of the sample mass in Table 1.
  • Control samples of Nature Works 2002D PLA and a maleated PLA are included as reference. The control samples were measured to contain less than 2.5% pentane by mass after impregnation, whereas materials containing the hydrophobic additives greatly increased the mass of pentane incorporated by the impregnation process.
  • the materials listed in Table 1 were subsequently expanded to produce foamed pellets by heating on a hot plate, allowing for liberation of the pentane blowing agent to the gas phase.
  • the present invention relates to the manufacture and use of compostable or biobased foamed beads.
  • the foamed beads of the present invention are used in the industry of manufacturing containers and other articles from compostable or biobased materials.

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Abstract

La présente invention concerne des billes expansées compostables ou d'origine biologique produites en coupant un fil expansé de base au niveau de la surface de la filière d'extrusion et la bille expansée ou le fil expansé de base est ensuite refroidi. Les billes expansées peuvent être utilisées pour fabriquer des articles en mousse. Les billes expansées sont produites au moyen d'un composé comprenant un polyester compostable ou d'origine biologique et un agent d'expansion. Des additifs, tels que des plastifiants ou des agents d'allongement de chaîne, sont éventuellement ajoutés à la composition compostable ou d'origine biologique.
EP12807830.0A 2011-07-07 2012-07-06 Mousses compostables ou d'origine biologique, et procédé de fabrication et d'utilisation Withdrawn EP2729521A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US13/178,293 US20120009420A1 (en) 2010-07-07 2011-07-07 Compostable or Biobased Foams
US13/178,300 US20120007267A1 (en) 2010-07-07 2011-07-07 Method of Producing Compostable or Biobased Foams
US13/178,272 US20120010307A1 (en) 2010-07-07 2011-07-07 Expandable Beads of a Compostable or Biobased Thermoplastic Polymer
US13/230,158 US8962706B2 (en) 2010-09-10 2011-09-12 Process for enabling secondary expansion of expandable beads
PCT/US2012/045723 WO2013006781A2 (fr) 2011-07-07 2012-07-06 Mousses compostables ou d'origine biologique, et procédé de fabrication et d'utilisation

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CN112074563B (zh) * 2018-03-12 2023-01-20 耐克创新有限合伙公司 热塑性泡沫物品
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WO2013006781A3 (fr) 2013-04-04
EP2729521A4 (fr) 2016-03-16
ZA201400868B (en) 2015-06-24
CA2841130A1 (fr) 2013-01-10
WO2013006781A2 (fr) 2013-01-10
CA2778580A1 (fr) 2013-01-07
AU2012278774A1 (en) 2014-02-27
JP2013018959A (ja) 2013-01-31
WO2013006781A9 (fr) 2013-05-23
MX2012003108A (es) 2013-02-07
CN103890066A (zh) 2014-06-25

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