Recyclable, biodegradable, and industrially compostable foams and methods for their manufacture

Abstract

A process for producing flexible foams includes introducing a polymer into an autoclave chamber or mold cavity, pressurizing the autoclave chamber or mold cavity to a high pressure using a supercritical fluid, maintaining the high pressure in the autoclave chamber or mold cavity for a time sufficient to infuse the supercritical fluid into the polymer, reducing the pressure in the autoclave chamber or mold cavity to allow the injected supercritical fluid to form cellular nuclei throughout the polymer, and expanding the cellular nuclei to form a foam from the polymer in the autoclave chamber or mold cavity. The polymer is composed of one or more non-crosslinked thermoplastic polymers that are recyclable and / or biodegradable. The polymer may be introduced into the autoclave chamber of the mold cavity as a solid sheet or block, or the polymer may be dissolved in a solvent.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Patent Application No. 63 / 486,291, filed February 22, 2023, and U.S. Patent Application No. 63 / 495,029, filed April 7, 2023, each of which is incorporated by reference herein in its entirety.

[0002] FIELD OF THE INVENTION The present disclosure, according to some embodiments, relates to processes for forming flexible foams from recycled, recyclable, biodegradable, bio-based, and / or industrially compostable materials. In some embodiments, the present disclosure provides an extrusion process for forming flexible foams. In some embodiments, the present disclosure provides an autoclave process for forming flexible foams. Foams produced according to embodiments of the present disclosure may be useful in a variety of industries and end products, including, but not limited to, footwear components, seating components, protective gear components, vehicle components, bedding, and watersports accessories. [Background technology]

[0003] background Flexible foams are a type of object formed by trapping pockets of gas in a liquid or solid, resulting in a foam that is said to be flexible in part due to its malleability. Flexible foams are typically used for cushioning applications, such as footwear, furniture, bedding, and other sporting goods. Flexible foams typically fall into two categories: closed-cell flexible thermoplastic polymer foams and open-cell flexible polyurethane foams. Each of these foam types has very different manufacturing methods.

[0004] Closed-cell flexible thermoplastic polymer foams are generally produced in a dry process, in which an appropriate synthetic polymer is selected and blended with various chemical additives, crosslinkers, and chemical foaming agents to produce a "dough." The dough is then kneaded and extruded into a flat sheet. The sheets are then stacked on top of each other and placed in a heated press under controlled pressure. This mixture of materials and chemical foaming agents react and expand inside the heated press cavity. The result is a closed-cell flexible foam "bun" or "block," which is then sliced ​​to thickness. In contrast, open-cell flexible polyurethane foams are generally produced in a liquid-casting or liquid-molding process, in which synthetic polyol chemicals, isocyanate chemicals, and other chemical additives are reacted together while being poured or injected into a molded shape, such as a "bun" or "block." The result is an open-cell flexible foam, which is then sliced ​​to thickness. Summary of the Invention [Problem to be solved by the invention]

[0005] The problem with flexible foams currently available on the market today is that they use mostly non-recyclable, non-compostable materials and / or environmentally harmful chemicals in their manufacture. Furthermore, due in part to the chemical crosslinking that occurs in the above-described methods of manufacturing conventional flexible foams, the physical structure of these flexible foams cannot be easily recycled or composted. This is primarily due to the chemical composition of the foam's design and its inability to be separated and returned to their original precursor components. That is, at the end of a conventional flexible foam's lifespan, the foam has no further use and cannot be successfully reprocessed into new materials in any known commercially viable manner. [Means for solving the problem]

[0006] overview The present disclosure, according to some embodiments, provides flexible foams and manufacturing processes that can be used to produce end products that are recyclable, biodegradable, compostable, sustainable, and / or environmentally responsible. In some embodiments, the foam materials and end products can be used sustainably without breaking, yet are easily recyclable and / or compostable at the end of their life.

[0007] An objective of the manufacturing processes disclosed herein is to result in an end product that is more environmentally responsible than more traditional manufacturing processes. By selecting recycled and / or recyclable or biodegradable and industrially compostable feedstocks for producing the polymer, embodiments of the present disclosure can contribute to the so-called circular economy and significantly reduce the amount of waste that ends up in landfills each year. In certain preferred embodiments, the flexible foam is derived from recycled materials and is recyclable at the end of its useful life. To that end, the selection of environmentally sustainable materials used in the manufacture of the end product should be carefully considered and balanced against the intended performance and useful life of the end product.

[0008] For example, running shoes are highly technical products that undergo repeated abuse, including all modes of impact, abrasion, and environmental exposure over a significant period of time, potentially one to three years depending on frequency of use. When selecting sustainable materials for use in manufacturing the sole, midsole, and / or insole cushioning of a running shoe, it is important to consider the above factors. Materials that cannot withstand repeated abuse before failing will not produce a satisfactory running shoe. Furthermore, materials that may break or degrade to the point of failure during normal product use before the end of their intended lifespan are unacceptable.

[0009] To address this issue, embodiments of the present disclosure utilize certain materials that offer a balance of technical performance characteristics as well as sustainability aspects. These sustainability aspects include, for example, properties such as recyclability or composability with controlled end-of-life solutions. In some embodiments, the materials used in the present disclosure are net-neutral (or negative) with respect to harmful emissions. Final products containing recyclable or compostable flexible foams manufactured according to embodiments of the present disclosure should perform very well over the life of the product, with only the end of the product's life having the option to be sent to a recycling or compost facility for a "closed-loop" waste diversion.

[0010] In certain embodiments, a process for producing flexible foam includes introducing a masterbatch material consisting essentially of one or more recycled, recyclable, biodegradable, and / or compostable thermoplastic polymers into an extruder, mixing an inert gas with the masterbatch material, extruding the masterbatch material through the extruder to form a polymer melt, passing the polymer melt through a die to form an extrudate, and expanding the extrudate into a foam. In some embodiments, the inert gas is nitrogen. In other embodiments, the inert gas is carbon dioxide.

[0011] In some embodiments, the one or more thermoplastic polymers are polyamides or polyamide copolymers. In some embodiments, the one or more thermoplastic polymers are polyamides selected from the group consisting of polyether block amide (PEBA), polyamide 6, polyamide 6 / 6-6, polyamide 12, or blends comprising one or more thereof. In some embodiments, the one or more thermoplastic polymers comprise polyesters or polyester copolymers. In some embodiments, the one or more thermoplastic polymers are selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), poly(L-lactic acid) (PLLA), poly(butylene adipate-co-terephthalate) (PBAT), polycaprolactone (PCL), polyhydroxy alkanoate (PHA), polyhydroxybutyrate (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate (PBA), thermoplastic starch (TPS), and the like. starch), and blends comprising one or more thereof. In some embodiments, the one or more thermoplastic polymers are or comprise one or more recycled polymeric materials. In some embodiments, the one or more thermoplastic polymers comprise one or more bio-derived polymers (e.g., bio-derived PBAT).

[0012] In some embodiments, the inert gas is mixed with the masterbatch material as a supercritical fluid. In some embodiments, the masterbatch material and the supercritical fluid are mixed to form a single-phase solution. In other embodiments, the inert gas is mixed with the masterbatch material before introducing the masterbatch material into the extruder. In some embodiments, the masterbatch material includes pellets of one or more thermoplastic polymers, and mixing the inert gas with the masterbatch material includes injecting the inert gas into the pellets of the one or more thermoplastic polymers. In some embodiments, injecting the inert gas into the pellets of the one or more thermoplastic polymers expands the pellets of the one or more thermoplastic polymers. In some embodiments, introducing the masterbatch material into the extruder includes introducing expanded pellets of the one or more thermoplastic polymers into the extruder. In some embodiments, extruding the masterbatch material through the extruder to form a polymer melt includes fusing the expanded pellets of the one or more thermoplastic polymers.

[0013] In some embodiments, a process for producing a flexible foam includes providing a plurality of pellets comprising one or more thermoplastic polymers that are recyclable, biodegradable, and / or industrially compostable; expanding the pellets of the one or more thermoplastic polymers by injecting an inert gas into the pellets; introducing the expanded pellets into an extruder; melting the expanded pellets in the extruder; and extruding the molten expanded pellets through a die using the extruder. In some embodiments, the one or more thermoplastic polymers are or include a polymer selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), poly(L-lactic acid) (PLLA), poly(butylene adipate-co-terephthalate) (PBAT), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate (PBA), thermoplastic starch (TPS), and blends comprising one or more thereof. In some embodiments, the one or more thermoplastic polymers are or include PBAT, PHA, and / or PHB. In some embodiments, the one or more thermoplastic polymers include one or more bio-based polymers. In some embodiments, the one or more thermoplastic polymers are recyclable polymers. The inert gas may be, for example, nitrogen or carbon dioxide. In some embodiments, the inert gas is injected into the pellets at a saturation pressure ranging from 75 bar to 200 bar, for example, from 90 bar to 150 bar. In some embodiments, the inert gas is injected into the pellets at a temperature ranging from 90°C to 200°C.

[0014] In some embodiments, a process for producing a flexible foam includes introducing a polymer into an autoclave chamber, pressurizing the autoclave chamber to a high pressure using a supercritical fluid, maintaining the high pressure in the autoclave chamber for a time sufficient to infuse the supercritical fluid into the polymer, reducing the pressure in the autoclave chamber to allow the injected supercritical fluid to form cellular nuclei throughout the polymer, and expanding the cellular nuclei to form a foam from the polymer in the autoclave chamber. The polymer is composed of one or more non-crosslinked thermoplastic polymers that are recyclable and / or biodegradable as described herein. The polymer can be introduced into the autoclave as a sheet or block. Alternatively, the polymer can be dissolved in an organic solvent and introduced into the autoclave in a liquid solution.

[0015] In some embodiments, a process for producing a foam includes introducing a polymer sheet or block into an autoclave chamber, pressurizing the autoclave chamber to a high pressure using a supercritical fluid, maintaining the high pressure in the autoclave chamber for a time sufficient to infuse the supercritical fluid into the polymer sheet or block, reducing the pressure in the autoclave chamber to cause the infused supercritical fluid to form cellular nuclei throughout the polymer sheet or block, and expanding the cellular nuclei to form a foam from the polymer sheet or block in the autoclave chamber. In some embodiments, the polymer sheet or block comprises one or more non-crosslinked thermoplastic polymers that are recyclable and / or biodegradable.

[0016] In some embodiments, the process for producing a foam further includes producing a polymer sheet or block by an extrusion process before introducing the polymer sheet or block into the autoclave chamber. In some embodiments, the extrusion process includes feeding pellets of one or more non-crosslinked thermoplastic polymers into an extruder, compressing and melting the pellets in the extruder to form a polymer melt, and extruding the polymer melt through a die. The extrusion process may also include cooling the polymer melt after it exits the die to form a solid polymer extrudate and cutting the solid polymer extrudate to form a polymer sheet or block. In some embodiments, the extrusion process further includes passing the solid polymer extrudate between rollers to flatten the solid polymer extrudate before cutting it.

[0017] In some embodiments, the process for producing a foam further includes producing a polymer sheet or block by an injection molding process before introducing the polymer sheet or block into the autoclave chamber. In some embodiments, the injection molding process includes, for example, forming a molten polymer from pellets of one or more non-crosslinked thermoplastic polymers, injecting the molten polymer into a mold having a predetermined shape and size, and cooling the molten polymer to solidify the polymer into a polymer sheet or block having the shape and size of the mold. In some embodiments, the predetermined shape of the mold is the shape of a shoe component, such as a shoe midsole or insole. In some embodiments, the foam has dimensions that are about 2 to about 3 times (e.g., 2.6 to 2.8 times) the dimensions of the polymer sheet or block.

[0018] In other embodiments, a process for producing a foam includes dissolving a polymer masterbatch comprising one or more recyclable and / or biodegradable non-crosslinked thermoplastic polymers in a solvent to form a solution, introducing the solution into an autoclave chamber, pressurizing the autoclave chamber to a high pressure using a supercritical fluid, maintaining the high pressure in the autoclave chamber for a time sufficient to dissolve the supercritical fluid in the solution, reducing the pressure in the autoclave chamber to cause the supercritical fluid to form cellular nuclei in the solution and evaporate the solvent from the solution, and expanding the cellular nuclei to form a foam from the solution in the autoclave chamber. The solvent may be an organic solvent. In some embodiments, the foam may be washed to remove residual solvent from the foam, and the foam may be dried after washing.

[0019] In some embodiments, the process utilizing the autoclave chamber further includes heating the autoclave chamber while pressurizing the autoclave chamber. In some embodiments, the autoclave chamber is heated above the critical temperature of the supercritical fluid, and the autoclave chamber is pressurized above the critical pressure of the supercritical fluid. In some embodiments, pressurizing the autoclave chamber to a high pressure using a supercritical fluid includes introducing a sufficient amount of supercritical fluid into the autoclave chamber to obtain a high pressure. In some embodiments, pressurizing the autoclave chamber to a high pressure using a supercritical fluid includes introducing an inert gas into the autoclave chamber and converting the inert gas into a supercritical fluid within the autoclave chamber. The supercritical fluid may be, for example, supercritical CO2, supercritical N2, or a mixture of the two.

[0020] In some embodiments, the pressure in the autoclave chamber is increased to at least 100 bar (10 MPa), at least 125 bar (12.5 MPa), at least 150 bar (15 MPa), at least 175 bar (17.5 MPa), or at least 200 bar (20 MPa). For example, the pressure in the autoclave chamber can be increased to about 180 bar (18 MPa) to about 200 bar (20 MPa). In some embodiments, the temperature in the autoclave chamber is increased to at least 75°C, at least 80°C, at least 85°C, at least 90°C, at least 95°C, at least 100°C, at least 105°C, at least 110°C, at least 115°C, at least 120°C, or at least 125°C. In some embodiments, for example, the temperature in the autoclave chamber is increased to about 95°C to about 115°C. In some embodiments, the high pressure and temperature are maintained in the autoclave chamber for more than 30 minutes, more than 60 minutes, at least 120 minutes, or at least 180 minutes, at least 240 minutes, at least 300 minutes, or at least 360 minutes (e.g., hold time) to infuse the supercritical fluid into the polymer sheet or block. In other embodiments, the hold time may be less than 15 minutes, less than 10 minutes, or less than 5 minutes. In some embodiments, the hold time is between 1 minute and 5 minutes, between 1 minute and 10 minutes, between 1 minute and 15 minutes, between 1 minute and 30 minutes, or between 1 minute and 60 minutes. In some embodiments, the hold time is between 60 minutes and 120 minutes. In some embodiments, the hold time is between 120 minutes and 180 minutes. In some embodiments, the hold time is between 180 minutes and 240 minutes. In some embodiments, the hold time is between 240 minutes and 300 minutes. In some embodiments, the hold time is between 300 minutes and 360 minutes.

[0021] In some embodiments, a further process for producing a foam includes placing a polymer sheet or block into a mold cavity, the polymer sheet or block comprising one or more non-crosslinked thermoplastic polymers that are recyclable and / or biodegradable; closing and sealing the mold cavity; heating the mold cavity to a predetermined temperature; introducing a sufficient amount of supercritical fluid into the mold cavity to pressurize the mold cavity; allowing the supercritical fluid to diffuse into the polymer sheet or block for a predetermined amount of time; and releasing the pressure in the mold cavity after the predetermined amount of time to expand the polymer sheet or block within the mold cavity. In some embodiments, the polymer sheet or block expands to substantially or completely fill the mold cavity. In some embodiments, the predetermined amount of time is sufficient for the diffusion of the supercritical gas into the solid polymer sheet or block to reach equilibrium. In some embodiments, the predetermined temperature is higher than the critical temperature of the supercritical gas. In some embodiments, the polymer sheet or block is an extruded polymer sheet or block. In some embodiments, the process includes manufacturing the polymer sheet or block by an extrusion process before placing the polymer sheet or block into the mold cavity, hi yet other embodiments, the process includes cooling the mold cavity before or simultaneously with releasing the pressure in the mold cavity.

[0022] In some embodiments, the one or more non-crosslinked thermoplastic polymers comprise one or more polymers derived from recycled feedstocks. In some embodiments, the one or more non-crosslinked thermoplastic polymers comprise polyamide or polyamide copolymer. In some embodiments, the one or more non-crosslinked thermoplastic polymers comprise a polymer selected from the group consisting of polyether block amide (PEBA), polyamide 6, polyamide 6 / 6-6, polyamide 12, or a blend comprising one or more thereof.

[0023] In some embodiments, the one or more non-crosslinked thermoplastic polymers are selected to be fully biodegradable and / or industrially compostable. In some embodiments, the one or more non-crosslinked thermoplastic polymers comprise a polymer selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), poly(L-lactic acid) (PLLA), poly(butylene adipate-co-terephthalate) (PBAT), polycaprolactone (PCL), polyhydroxyalkanoates (PHAs), polyhydroxybutyrate (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate (PBA), thermoplastic starch (TPS), and blends comprising one or more thereof. In some embodiments, the one or more non-crosslinked thermoplastic polymers comprise poly(butylene adipate-co-terephthalate) (PBAT). In some embodiments, the one or more non-crosslinked thermoplastic polymers consist solely of poly(butylene adipate-co-terephthalate) (PBAT). In some embodiments, the one or more non-crosslinked thermoplastic polymers comprise a bio-based polymer, such as a bio-based polyester. In some embodiments, the one or more non-crosslinked thermoplastic polymers comprise a branched polyester.

[0024] In some embodiments, the one or more non-crosslinked thermoplastic polymers are selected from the group consisting of poly(1,4-butylene adipate-co-1,4-butylene terephthalate), poly(1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene terephthalate), poly(1,4-butylene brassylate-co-1,4-butylene terephthalate), poly(1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene sebacate), and poly(1,4-butylene azelate-co-1,4-butylene terephthalate). poly(1,4-butylene adipate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene azelate-co-1,4-butylene terephthalate), poly(1,4-butylene succinate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate) ), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene brassylate-co-1,4-butylene sebacate-co-1,The one or more aliphatic-aromatic polyesters may each be a bio-based polyester, preferably biodegradable.

[0025] In some embodiments, foams made according to the processes described herein are recyclable, biodegradable, and / or compostable. The foams are preferably microcellular flexible foams that can be used in place of traditional crosslinked flexible foams. The method for producing foams according to certain preferred embodiments does not include a chemical crosslinking process or step. In some embodiments, the foams do not include crosslinking agents. In some embodiments, the foams do not include crosslinks or crosslinking agents that would prevent the foam from being recycled or biodegraded. A crosslink is a bond or short series of bonds that connects one polymer chain to another. Such bonds, if present, can prevent a polymeric material from being easily recycled and / or biodegraded. Therefore, the polymers used in the embodiments described herein are preferably not crosslinked (also referred to as "non-crosslinked" or "uncrosslinked"). Therefore, non-crosslinked foams according to some embodiments should not contain or be formed from crosslinked polymers. In further embodiments, foams made according to the processes described herein may be molded and used to manufacture various articles such as, but not limited to, footwear components (e.g., shoe insoles or midsoles), seating components (e.g., seat cushions), protective gear components (e.g., padding), vehicle components, bedding components, water sports accessories, or other end products that include foam components.

[0026] BRIEF DESCRIPTION OF THE DRAWINGS The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention may be embodied in different forms and, therefore, should not be construed as limited to the embodiments set forth herein. The accompanying drawings may not be drawn to scale. [Brief explanation of the drawings]

[0027] [Figure 1] 1 is a flowchart of a process for forming an extruded flexible foam according to some embodiments of the present disclosure. [Figure 2] FIG. 1 illustrates a system for forming extruded flexible foam according to some embodiments of the present disclosure. [Figure 3] FIG. 1 illustrates another system for forming extruded flexible foam according to some embodiments of the present disclosure. [Figure 4] FIG. 1 illustrates another system for forming extruded flexible foam according to some embodiments of the present disclosure. [Figure 5] 1 is a flowchart of a process for forming a flexible foam using an autoclave, according to some embodiments of the present disclosure. [Figure 6] 1 is a flow chart of a second process for forming a flexible foam using an autoclave according to a further embodiment of the present disclosure. [Figure 7] 10A-10C illustrate a comparison of the relative sizes of preformed polymer blocks in the shape of a shoe midsole before and after foaming in accordance with an exemplary embodiment. [Figure 8] FIG. 1 illustrates an autoclave system for producing foams according to some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0028] Detailed Description The present disclosure provides, in some embodiments, recyclable, biodegradable, and / or industrially compostable flexible foams and methods for their manufacture. Foams according to embodiments of the present disclosure may be closed-cell foams. In other embodiments, foams according to the present disclosure may be open-cell foams. In some embodiments, foams produced according to the methods of the present disclosure are microcellular flexible foams useful in various products as a replacement for traditional ethylene vinyl acetate or polyurethane foams. In various embodiments, recyclable, biodegradable, and / or industrially compostable flexible foams can be made to have properties and performance characteristics similar to traditional non-recyclable ethylene vinyl acetate (EVA) foams or thermoplastic polyurethane (TPU), but with a higher percentage of recycled or bio-based content. Foams produced according to embodiments of the present disclosure may be useful in various industries and end products, including, but not limited to, footwear components, seating components, protective gear components, vehicle components, bedding, and watersports accessories.

[0029] As used herein, "biodegradable" generally refers to the ability to be broken down by biological activity, particularly microorganisms. In some embodiments, materials and foams described herein as biodegradable and / or industrially compostable meet or exceed the requirements set forth in at least one of the following standards: European Standard EN 13432, ASTM D6400, or Australian Standard AS4736. In some embodiments, materials and foams described herein as biodegradable and / or industrially compostable meet or exceed the requirements set forth in at least European Standard EN 13432. In some embodiments, materials and foams described herein as industrially compostable are configured to exhibit at least 60% biodegradation within 180 days of composting in a commercial composting unit (at least 60% of the material must be degraded by biological activity). In some embodiments, materials and foams described herein as industrially compostable are configured to exhibit at least 90% biodegradation within 180 days of composting in a commercial composting unit.

[0030] In some embodiments, the term "recyclable" can generally refer to the ability of a material or product to be collected, separated, or otherwise recovered from a waste stream for reuse or use in the manufacture or assembly of another article. In some embodiments, polymers and foams described herein as being recyclable refer to the ability of the constituent materials to be recovered, for example, by mechanical recycling, chemical recycling, and / or biological or organic recycling. In some embodiments, polymers and foams described herein as being recyclable refer to the ability to depolymerize the polymers and foams, for example, to recover the constituent monomers that form the polymers and foams. In some embodiments, polymers and foams described herein as being recyclable refer to the ability of the constituent materials to be recovered using standard plastic recycling methods, for example, as described in ISO 15270:2008. In some embodiments, recycled materials, foams, and / or products described herein can be manufactured in accordance with the requirements set forth in the Recycled Claim Standard 2.0 (RCS, dated July 1, 2017) and / or the Global Recycle Standard 4.0 (GRS, dated July 1, 2017).

[0031] In some embodiments, a process for forming an extruded flexible foam according to the present disclosure generally includes introducing polymer pellets into an extruder, melting the polymer pellets in the extruder to form a polymer melt, and extruding the polymer melt through a die to form an extrudate. In some embodiments, a blowing agent is introduced into the extruder and mixed with the polymer melt. In some embodiments, the blowing agent is introduced as a supercritical fluid and forms a single-phase solution with the polymer melt. In other embodiments, the polymer pellets are saturated with a foaming agent before being introduced into the extruder. As further described herein, the polymer pellets are preferably composed of one or more thermoplastic polymers that are recyclable, biodegradable, and / or industrially compostable. In some embodiments, the polymer pellets are composed of a bio-based thermoplastic polymer. In some embodiments, the polymer pellets are made from recycled plastic materials.

[0032] FIG. 1 is a flowchart of a process 100 for forming extruded flexible foam according to certain exemplary embodiments of the present disclosure. In step 102, in some embodiments, process 100 includes providing a masterbatch of one or more preselected materials. In some embodiments, the masterbatch is comprised of a thermoplastic polymer material in the form of pellets, granules, or the like. As noted above, the one or more preselected materials are preferably, according to some embodiments, one or more thermoplastic polymers that are recyclable, biodegradable, and / or industrially compostable. In some embodiments, the one or more preselected materials are derived from recycled plastic waste materials. In some embodiments, the masterbatch is comprised entirely of one or more preselected biodegradable materials (e.g., biodegradable thermoplastic polymers). In some embodiments, the masterbatch is comprised entirely of one or more preselected recyclable materials (e.g., recyclable thermoplastic polymers).

[0033] In step 104 of process 100, an inert gas is mixed with the masterbatch. In some embodiments, the inert gas (e.g., a blowing agent) is mixed with the masterbatch in one or more extruders. In some embodiments, the inert gas may be mixed with the masterbatch as a supercritical fluid. In some embodiments, the masterbatch melts and forms a single-phase solution with the supercritical fluid. In other embodiments, the masterbatch is saturated with the inert gas (e.g., a foaming agent) before introducing the masterbatch into one or more extruders.

[0034] In some embodiments, saturating the masterbatch pellets with an inert gas injects a portion of the gas into the pellets, causing the pellets to at least partially expand. In some embodiments, saturating the masterbatch with an inert gas forms puffed or at least partially expanded polymer pellets, which can then be fused together (e.g., by extrusion). In some embodiments, the puffed polymer pellets have a size (e.g., in their largest dimension) of 4 mm to 10 mm. In some embodiments, the puffed polymer pellets have a bulk density of about 100 kg / m. 3 ~about 200kg / m 3In some embodiments, the polymer pellets have an expansion ratio ranging from about 1.5 to about 4.5. In some embodiments, the inert gas saturation pressure can range from 75 bar to 200 bar, e.g., from 90 bar to 150 bar. In some embodiments, the inert gas saturation temperature can range from 90°C to 200°C, depending on the liquid point and melting temperature of the particular biodegradable, industrially compostable, and / or recycled and / or recyclable polymer. Furthermore, in some embodiments, the average pore size and cell density of the foam can be controlled to some extent by adjusting the saturation pressure. In some embodiments, a high inert gas saturation pressure is preferred to achieve a small average pore size and a high cell density. In still further embodiments, the polymer may be optionally pre-dried and dehumidified prior to foaming. In some embodiments, for example, pre-drying conditions are a temperature range of 65-85°C with a dew point of -40°C and a relative humidity of less than 0.05% for 4-6 hours.

[0035] In step 106, the masterbatch mixed with the gas forms a polymer melt, which is extruded through one or more extruders. The one or more extruders may be, for example, screw extruders having one or more extrusion screws for compressing and conveying the polymer melt. In step 108, the polymer melt is extruded into a sheet of microcellular foam. In some embodiments, the polymer melt is extruded through a die configured to shape the extrudate. In some embodiments, as the polymer melt is extruded through the die, the gas mixed within the polymer melt expands, resulting in a flexible foam. In further embodiments, the flexible foam can then be cut and / or shaped (e.g., via compression molding) into any desired configuration.

[0036] The present subject matter is described more fully below, where exemplary embodiments are described. However, the present subject matter may be embodied in different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain and enable those skilled in the art to practice the present subject matter.

[0037] thermoplastic polymer In some embodiments, creating microcellular extruded foam from recycled and / or recyclable thermoplastic polymers, or even bio-based thermoplastic polymers, begins with selecting an appropriate high-performance polymer. Suitable thermoplastic polymers that can be utilized according to embodiments of the present disclosure should preferably include the following properties: produce low-density foams, have a moderate melt flow rate, produce high elongation upon foaming, and be 100% recyclable and / or 100% industrially compostable. In some non-limiting examples, suitable thermoplastic polymers produce foams with densities between 0.15 g / cc and 0.35 g / cc, preferably between 0.20 g / cc and 0.25 g / cc. In some non-limiting examples, suitable thermoplastic polymers have melt flow rates ranging from 5 g / 10 min to 30 g / 10 min, preferably between 10 g / 10 min and 20 g / 10 min. In other examples, the melt flow rate may range from 7 g / 10 min to 15 g / 10 min. In some non-limiting examples, suitable thermoplastic polymers provide foam elongation in the range of 150% to 800%, preferably 250% to 450%. In some embodiments, the thermoplastic polymer may be provided in the form of solid pellets sized and configured to be fed into an extruder. A plurality of pellets of polymeric material fed into an extruder may be referred to herein as a "masterbatch." In certain preferred embodiments, the polymeric material selected for the pellets is not crosslinked.

[0038] In some embodiments, the thermoplastic polymer used to produce the recyclable, biodegradable, and / or industrially compostable flexible foams of the present disclosure can be selected from any number of polyamides or polyamide copolymers. Non-limiting examples of suitable polyamide polymers include polyether block amide (PEBA), polyamide 6, polyamide 6 / 6-6, polyamide 12, and blends containing one or more thereof. A non-limiting example of a suitable recycled and / or recyclable polymer is PEBA manufactured by Nylon Corporation of America (Manchester, New Hampshire).

[0039] In some embodiments, the thermoplastic polymer used to produce the recyclable, biodegradable, and / or industrially compostable flexible foams of the present disclosure can be selected from any number of polyesters, including polyester copolymers, preferably bio-based polyesters. In some embodiments, the thermoplastic polymer is or includes a branched polyester. Non-limiting examples of suitable polymers include polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), poly(L-lactic acid) (PLLA), poly(butylene adipate-co-terephthalate) (PBAT), polycaprolactone (PCL), polyhydroxyalkanoates (PHAs), polyhydroxybutyrate (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate (PBA), thermoplastic starch (TPS), and blends comprising one or more thereof. In some embodiments, the thermoplastic polymer selected for the recyclable, biodegradable, and / or industrially compostable flexible foams of the present disclosure comprises or consists solely of PBAT, hi some embodiments, the thermoplastic polymer selected for the recyclable, biodegradable, and / or industrially compostable flexible foams of the present disclosure comprises or consists solely of PHA.

[0040] In some embodiments, the thermoplastic polymer used to produce the foams of the present disclosure comprises a biodegradable polyester. In some embodiments, the biodegradable polyester is a branched polyester. In some embodiments, the biodegradable polyester is selected from aliphatic biodegradable polyesters and aliphatic-aromatic biodegradable polyesters. In some embodiments, the biodegradable polyester is an aliphatic-aromatic polyester. According to some embodiments, the aliphatic-aromatic polyester can have an aromatic portion comprising a polyfunctional aromatic acid and an aliphatic portion comprising an aliphatic diacid, an aliphatic diol, and mixtures thereof. According to some embodiments, the aliphatic-aromatic polyester can have from about 30% to about 70% by mole, for example, from about 40% to about 60% by mole, of aromatic acid.

[0041] In some embodiments, the polymer used in the foams of the present disclosure is poly(1,4-butylene adipate-co-1,4-butylene terephthalate), poly(1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene terephthalate), poly(1,4-butylene brassylate-co-1,4-butylene terephthalate), poly(1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene sebacate). to-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene azelate-co-1,4-butylene terephthalate), poly(1,4-butylene succinate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate to-co-1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate) ), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene brassylate-co-1,4-butylene sebacate-co-1,The aliphatic-aromatic polyester may comprise one or more aliphatic-aromatic polyesters selected from the group consisting of poly(1,4-butylene adipate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene sebacate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate). In certain preferred embodiments, the aliphatic-aromatic polyester is poly(1,4-butylene adipate-co-1,4-butylene terephthalate) or poly(1,4-butylene adipate-co-1,4-butylene azelate-co-1,4-butylene terephthalate). In some embodiments, the polymer used in the foams of the present disclosure may comprise a mixture of two or more different polyesters described herein.

[0042] In some embodiments, recycled feedstocks are used to produce suitable recyclable polymers or polymer blends of the present disclosure. An objective of certain embodiments is to use recycled polymer feedstocks whenever possible. Examples of using recycled feedstocks include, according to some embodiments, post-industrial polyamide carpet fibers, recovered ocean plastic fishing nets, or other plastic waste materials that have been collected, sorted, melted, and reprocessed. In some such examples, the collected waste materials can be reprocessed into virgin-quality polyamide precursors (e.g., caprolactam). An exemplary caprolactam derived from post-industrial carpet fibers and used fishing nets is Econyl, manufactured by Aquafil USA, Inc. (Cartersville, Georgia). The aforementioned thermoplastic polymer resins exhibit advantageous technical properties in forming optimal microcellular flexible foam structures according to embodiments of the present disclosure. Some of these technical properties include, among other benefits, excellent aging properties, excellent elongation, tensile strength, and compression set.

[0043] Furthermore, in some embodiments, bio-based polymers are used to manufacture the flexible foams of the present disclosure. In some embodiments, the terms "bio-based" or "biopolymer" or "bioplastic" may be used interchangeably herein to refer to polymers derived from current, preferably renewable, biological sources (e.g., as opposed to petroleum-based or other fossil fuel-based sources) or made from precursor materials (e.g., reactants, monomers, etc.) derived from such current biological sources. In some such embodiments, the biological source may be a renewable botanical (plant) source. For example, the bio-based polymer or its precursor materials may be derived from plant cellulose, plant oil, and / or other plant materials. In some embodiments, the bio-based polymer is or includes one or more of the polyesters described above, such as one or more aliphatic-aromatic polyesters. In some embodiments, the bio-based polymer includes one or more branched polyesters. One non-limiting example of a biopolymer suitable for use in the present disclosure is bio-based PBAT. In some embodiments, the bio-based PBAT is biodegradable and industrially compostable. In some embodiments, bio-based PBAT can be formed from precursors including azelaic acid and bio-based biobutanediol (bio-BDO). One or more biopolymers used in the production of foams (e.g., bio-based PBAT, bio-based branched polyesters, or other bio-based aliphatic-aromatic polyesters) exhibit overall advantageous technical properties in forming optimal microcellular flexible foam structures according to embodiments of the present disclosure. Some of these technical properties include, among other benefits, excellent aging properties, excellent elongation, tensile strength, and compression set. In addition to plants, in some embodiments, biological sources of "biological" or "biopolymer" or "bioplastic" materials include, for example, microorganisms (e.g., bacteria), algae, fungi, animals (e.g., animal fats / lipids), and / or insects.

[0044] In some embodiments, blends of two or more thermoplastic polymers can be utilized. In some embodiments, blends of two or more thermoplastic polymers can provide a combination of properties not found in a single polymer. There are several ways to successfully blend polymers. One such method is to melt two or more polymer resins together using a twin-screw extruder, then extrude the molten polymer resin blend into strands, cool the strands, and feed them into a pelletizer to produce an array of pelletized pieces called a masterbatch. Another method of polymer blending is to use a compatibilizer to combine different polymers into a polymer blend. This method can also be achieved by melting the compatibilizer and two or more polymers together to form a blend, such as using a twin-screw extruder.

[0045] additives In certain embodiments, one or more additives may be optionally added to the polymer formulation depending on the application. The one or more additives may include, for example, one or more fillers, nucleating agents, and / or colorants. In some embodiments, one or more additives may be included to adjust the physical and / or chemical properties of the resulting foam. Preferably, in some embodiments, the one or more additives include or consist of recyclable and / or compostable materials. In some embodiments, one or more biodegradable and / or recyclable binders are optionally included to aid in fusing the expanded pellets together. In some embodiments, the one or more additives may be added to the polymer prior to extrusion (e.g., mixed with a masterbatch). In some embodiments, the one or more additives may additionally or alternatively be added to an extruder and mixed with the polymer within the extruder (e.g., via a side feed to the extruder).

[0046] In some embodiments, one or more fillers may be optionally added to the polymer to reduce part costs. For example, in some embodiments, one or more fillers have a lower cost per weight than the polymer material and may be used to add physical bulk to the product and / or improve certain properties. In some non-limiting examples, the one or more fillers, if included, may be added at a loading weight ratio ranging from 1% to 30%. The one or more fillers may include, for example, precipitated calcium carbonate, roe-like aragonite, starch, biomass, etc. In some embodiments, the material of the one or more fillers is selected so that the flexible foam and / or the final product remain recyclable and / or compostable.

[0047] In some embodiments, a nucleating agent, such as microlayered talc or high-aspect-ratio oolitic aragonite, can be included. In certain embodiments, the nucleating agent can significantly improve important properties of the resulting flexible foam by preventing cell coalescence (e.g., bubble merging), reducing bulk density, and improving resilience, among other beneficially enhanced properties. In some such embodiments, the nucleating agent improves foaming by increasing the amount of individual cells in the foam material. Some non-limiting examples of nucleating agents for use in producing flexible foams include microlayered talc sold as Mistrocell® by Imerys Talc America, Inc. (Houston, Texas) and high-aspect-ratio oolitic aragonite sold as OceanCal® by Calcean Minerals & Materials, Inc. (Gadsden, Alabama). In some non-limiting examples, one or more nucleating agents, if included, may be added at a loading weight ratio ranging from 0.1% to 10%.

[0048] In further embodiments, one or more additives configured to promote and / or improve biodegradation of the finished foam product may be included. In one example, oligomeric poly(aspartic acid-co-lactide) (PAL) may be optionally incorporated into the masterbatch to promote biodegradation as needed in certain cases and for certain end-market applications.

[0049] In some embodiments, one or more colorants may be optionally included to alter the color of the resulting flexible foam. For example, various colorants, such as dyes or pigments, may be optionally included in the polymer formulations of the present invention. Some non-limiting examples are pigments tailored for use with specific types of thermoplastic polymers, such as those offered by Treffert (Bingen am Rhein, Germany) or Holland Colors Americas (Richmond, Indiana). In some non-limiting examples, the colorant(s), if included, may be added at a weight loading of 0.1% to 5%.

[0050] Foaming and foaming agents To produce foams by certain processes of the present disclosure, the polymer formulation is mixed with a blowing agent. A widely known blowing agent used in conventional manufacturing processes is azodicarbonamide (ADA). ADA is often used as a chemical foaming agent and is typically pre-impregnated into conventional thermoplastic masterbatch resins for use in conventional injection molding foaming processes. However, ADA is not considered environmentally friendly and is a suspected human health carcinogen. Furthermore, conventional foaming processes using ADA typically produce foams that are crosslinked during the manufacturing process and therefore are not recyclable or compostable. Therefore, in preferred embodiments, the process of the present disclosure does not use ADA. Crosslinking agents are not incorporated into the foams of certain embodiments of the present disclosure.

[0051] Processes according to embodiments of the present disclosure can utilize one or more inert physical foaming agents instead of chemical foaming agents. In some embodiments, an inert gas is used as the foaming agent for the foaming process of the present disclosure. In some embodiments, the foaming agent used in embodiments of the present disclosure is either nitrogen gas (N) or carbon dioxide (CO). In some embodiments, the foaming agent is introduced to the polymeric material as a supercritical fluid (SCF). For example, the SCF can include or consist of supercritical N or supercritical CO. In some embodiments, the SCF and polymeric material form a single-phase solution. In some embodiments, the foaming process of the present disclosure includes passing a single-phase solution of polymer and supercritical fluid (SCF) through an extrusion die to form a continuous extrudate. In some embodiments, the extrudate has an annular shape. In some embodiments, the extrudate is formed into a flat sheet. Other shapes are possible according to other embodiments. In some embodiments, uniform cell nucleation occurs as the single-phase solution of polymer and supercritical fluid (SCF) passes through the extrusion die. In some embodiments, as the solution exits the extrusion die, the pressure is reduced, causing the SCF to come out of solution and create cell nuclei (e.g., gas bubbles). The cells then grow until the material expands, consuming the expansion capacity of the SCF, thereby stabilizing the resulting foam. As further described herein, processes according to some embodiments can be carried out in an extrusion machine modified to allow for the metering, delivery, and mixing of an inert SCF into the polymer to create a single-phase solution.

[0052] The difference in effectiveness of nitrogen and carbon dioxide as blowing agents stems from their behavior in polymer melts. Carbon dioxide, which becomes a supercritical fluid at temperatures and pressures above its critical point (approximately 31 °C and approximately 73 bar), is four to five times more soluble in polymers than nitrogen, which becomes a supercritical fluid at approximately -147 °C and approximately 34 bar. For example, the saturation point of an unfilled polymer is approximately 1.5 to 2% (by weight) nitrogen, depending on temperature and pressure conditions, while the saturation level for carbon dioxide is closer to 8% (by weight). Carbon dioxide also exhibits greater mobility in polymers, allowing it to migrate further into existing bubbles than nitrogen. From a cell nucleation perspective, greater solubility and mobility mean fewer cells nucleate, and the cells that do nucleate tend to be larger.

[0053] However, solubility can be an advantage in certain embodiments when viscosity reduction is the goal. In some embodiments, lower viscosity can be beneficial for lower part weights. In some embodiments, SCF dissolved in a polymer acts as a plasticizer, reducing the viscosity of the polymer. Because viscosity reduction is partially proportional to the amount of SCF added to the polymer, and because carbon dioxide has a higher solubility limit than nitrogen, the viscosity reduction potential of carbon dioxide is greater.

[0054] In some embodiments, carbon dioxide is also preferred as a blowing agent when the amount of nitrogen required to produce a part is too low to consistently process the part. In some embodiments, given that carbon dioxide has a higher solubility in polymers than nitrogen, it may be easier to flow low levels of carbon dioxide, such as 0.15 or 0.2%, compared to very low levels of nitrogen, such as less than 0.05%. This occurs primarily with soft materials and parts with thick cross sections.

[0055] In some alternative embodiments, one or more foaming agents are used to pre-expand pre-expanded pellets of polymeric material. In some embodiments, the foaming agent is an inert gas. In some such embodiments, the foaming agent may be either nitrogen or carbon dioxide. In some embodiments, pre-expansion involves injecting a gas (e.g., nitrogen or carbon dioxide) into the polymeric pellets, thereby forcing their individual expansion to form pre-expanded expanded pellets. In some embodiments, these pre-expanded pellets are extruded into a continuous sheet in various thicknesses and lengths to meet given needs. The finished fused pellet sheet is the result of fusing the individual pre-expanded pellets into multiple expanded and fused pellets. The finished uniform sheet is then ready for die-cutting or molding by conventional means as known in the art.

[0056] In further embodiments, the SCF may be mixed with the polymeric material in an autoclave configured to operate at a predetermined pressure and temperature. The autoclave may include, for example, a chamber pressurized by the SCF for a time sufficient to mix the SCF with the polymeric material. As described in more detail below, subsequent depressurization of the chamber causes the SCF to form cellular nuclei (e.g., gas bubbles) in the polymeric material, which expand to form a foam. In some embodiments, the polymeric material is introduced into the autoclave as an unfoamed solid block or sheet (e.g., an extruded block or sheet). In other embodiments, the polymeric material may be dissolved in a solvent and introduced into the autoclave in solution. The autoclave may be maintained at the pressure and temperature for a hold time sufficient to saturate the polymeric material and subsequently depressurize to foam the polymeric material.

[0057] Extrusion System According to some aspects, the present disclosure provides a system for producing recyclable, biodegradable, and / or industrially compostable flexible foam. In various embodiments, the system may include one or more of the following components: at least one extruder configured to melt and convey a polymeric material, a hopper configured to introduce the polymeric material (e.g., in the form of pellets) into the extruder, and a die for shaping the material extruded by the extruder. In some embodiments, the aforementioned components may be combined into a single device. In some embodiments, the system according to the present disclosure further includes a gas source configured to provide a blowing or frothing agent (e.g., nitrogen or carbon dioxide) that is mixed with the polymeric material. In some embodiments, the system further includes a control system configured to control various process parameters of the extrusion system, such as, but not limited to, one or more of temperature, pressure, polymer feed rate, gas injection, or extrusion rate.

[0058] In some embodiments, the at least one extruder may be a screw extruder. In some such embodiments, the screw extruder includes a barrel and at least one screw disposed within the barrel and configured to rotate therein. In some embodiments, the at least one screw is configured to compress, melt, and convey polymeric material introduced into the extruder. In some embodiments, a hopper may be included for feeding a polymer masterbatch (e.g., pelletized polymeric material) into the barrel of the extruder. In some embodiments, the polymer masterbatch may be gravity-fed from the hopper through a throat of the hopper into the barrel and screw assembly of the extruder.

[0059] In some embodiments, at least one screw may be driven by one or more motors. In some embodiments, the screw extruder is a multiple screw extruder having two or more rotating screws. In some such embodiments, the screw extruder may be a twin screw extruder having a pair of intermeshing parallel screws. In further embodiments, the screw may be a reciprocating screw. The reciprocating screw may include three zones: a feed zone, a compression (or transition) zone, and a metering zone. In some embodiments, the system includes at least two extruders. In some embodiments, the system includes a first melt extruder that feeds material to a second cooling extruder.

[0060] In some embodiments, a nozzle may be present that connects the extruder barrel to the die and forms a seal between the barrel and the die. In some embodiments, the temperature of the nozzle may be set at or just below the melting temperature of the polymer material. In some embodiments, the die includes a sprue bushing, and the nozzle connects to the sprue bushing. In some embodiments, a delivery system may also be included. In some embodiments, the delivery system provides a passage for the molten polymer from the nozzle to the die and generally may include a sprue, a cold slug well, a main runner, branch runners, a gate, or the like. In some embodiments, when the barrel is in its full forward processing position, the radius of the nozzle may nest and seal with a recessed radius in the sprue bushing with a positioning ring. During barrel purging (cleaning), the barrel may retract from the sprue, allowing the purge compound to freely fall from the nozzle.

[0061] In a further aspect, the system may further include a supercritical fluid (SCF) injection system configured to receive a gas (e.g., nitrogen or carbon dioxide) and introduce the received gas into the barrel of the extruder under conditions that generate a supercritical fluid upon introduction. In some embodiments, the supercritical fluid injection system may be configured to modify the pressure and / or temperature of the received gas to exceed the critical point of the gas. In some embodiments, for example, the SCF injection system may include a source of gas (e.g., nitrogen or carbon dioxide), an air compressor, an SCF metering and control device, an SCF injector, and a front and rear check valve. In some embodiments, the supercritical fluid mixes with the thermoplastic polymer in the barrel of the extruder. In some embodiments, the supercritical fluid and the thermoplastic polymer form a single-phase solution in the barrel of the extruder. In some embodiments, the formation of a single-phase solution in which the SCF is completely dissolved and uniformly dispersed in the molten polymer occurs inside the extruder barrel under carefully controlled process conditions. In some embodiments, the SCF must be precisely metered in mass flow to the polymer over a period of time, and specific conditions of temperature, pressure, and shear must be established in the barrel during the injection period. In some embodiments, back pressure, screw speed and barrel temperature controls, and the SCF dosing system all play a role in establishing process conditions that produce a single-phase solution.

[0062] In some embodiments, the process setup procedure centers around establishing controlled SCF input into the extruder barrel under screw speed, temperature, and pressure conditions that result in a single-phase solution. In some embodiments, one or more of the following system parameters can be adjusted to ensure that the basic conditions for SCF input are met:

[0063] 1) SCF Saturation Pressure: In some embodiments, the effects of inert gas saturation pressure and saturation temperature play a significant role in the expansion ratio of the foam. In some non-limiting examples, the saturation pressure can range from 75 bar to 200 bar, preferably from 90 bar to 150 bar. The inert gas saturation temperature can range, for example, from 90°C to 200°C, depending on the dropping point and melting temperature of a particular biodegradable, industrially compostable, and / or recyclable polymer. Furthermore, the average pore size and cell density of the foam can be controlled to some extent by adjusting the saturation pressure (the pressure at which the inert gas saturates the selected polymer). High inert gas saturation pressures are preferred in some embodiments to achieve small average pore sizes and high cell densities. The effects of inert gas saturation pressure and saturation temperature play a significant role in the expansion ratio of the foam.

[0064] 2) SCF Injector Open Position: This set point establishes the screw position where SCF injection begins. This position should be set so that the pressure in the barrel during screw recovery stabilizes before injection begins. As a non-limiting example, the open position can range from 0.3 inches to 0.4 inches.

[0065] 3) SCF Percentage: This controls the actual mass of SCF added. Non-limiting examples of SCF percentage can be in the range of 0.45% to 0.75%, more preferably 0.5%.

[0066] 4) Optimizing injection: This is achieved by maximizing injection time and minimizing flow rate (pressure difference between pre-metering pressure and delivery pressure). Non-limiting examples of injection times are 1-2 seconds, more preferably 1.7 seconds. In some embodiments, a single polymer melt is nucleated within the die and discharged as a single polymer melt stream at the die exit, whereby the discharge time is preferably a fraction of a second.

[0067] In some embodiments, once a single-phase solution is produced, the extruder maintains the solution under pressure until extrusion begins. In some embodiments, the extruder does this through the coordination of a pressure regulating valve and a melt pump control. In some embodiments, the pressure regulating valve prevents pressure reduction and premature foaming in the die elements. In further embodiments, either active or passive screw position control can be utilized to prevent pressure reduction due to screw backflow. According to some such embodiments, during active screw position control, the screw position is continuously monitored, and the pressure applied to the back of the screw is adjusted to maintain a position setpoint, or a constant pressure is maintained at the back of the screw. In passive position control, oil can be used to regulate backpressure, preventing oil from being discharged to its tank at the end of screw recovery. This residual oil prevents the screw from moving backward due to the pressure of the single-phase solution.

[0068] In some embodiments, the disclosed systems may further include one or more temperature sensors configured to monitor and / or control the temperature within the barrel or other system components. In some embodiments, the systems may include one or more pressure sensors configured to monitor and / or control the pressure within the barrel or other system components. Additionally, a control unit having one or more microprocessors may be included, configured to control one or more of the extruder and the supercritical gas input system according to one or more system parameters. In some embodiments, the control system may be configured to provide consistency and repeatability in extruder operation. In some embodiments, the control system monitors and controls process parameters including temperature, pressure, SCF input, injection rate, screw speed and position, and hydraulic position. Control systems can range from simple relay on / off control to highly sophisticated microprocessor-based closed-loop control.

[0069] In some embodiments, the system and / or any of its subsystems can include one or more sensors, such as a temperature sensor, a pressure sensor, an accelerometer, a gyroscope, and an orientation sensor. In some embodiments, the one or more sensors are configured to be positioned to communicate with one or more of the other components of the extrusion system, such as in the extruder, the die, etc. In various embodiments, the one or more sensors can be smart sensors and can include a communications module configured to connect to a network. In some embodiments, the communications module can be further configured to perform wireless communications. In some embodiments, the system, and / or any of its various portions can include a communications module that can be coupled to one or more of the control system, the SCF dosing system, and the gas back pressure control unit; for example, the communications module is configured to perform one or more wireless communications protocols, including WIFI, Bluetooth, low-energy Bluetooth, and 3G, 4G, and 5G cellular communications.

[0070] FIG. 2 illustrates a system 200 for manufacturing flexible foam, according to one non-limiting example. In some embodiments, in a first stage, the system 200 includes a pressure vessel 202 configured to contain pellets of a masterbatch 204. The pellets may be composed of any one or more of the non-limiting examples of thermoplastic polymer materials described above. For example, the pellets may be composed entirely of one or more recyclable thermoplastic polymers or entirely of one or more biodegradable thermoplastic polymers (e.g., one or more biopolymers). In some embodiments, for example, the pellets of the masterbatch 204 include or consist of PBAT (e.g., bio-derived PBAT). In some embodiments, the pellets include or consist of the biodegradable branched polyesters described above or other aliphatic-aromatic polyesters. In some embodiments, the pellets of the masterbatch 204 can be infused or saturated with an inert gas (e.g., carbon dioxide or nitrogen) within the pressure vessel 202.

[0071] In some embodiments, the influence of the saturation pressure and saturation temperature of the inert gas (e.g., in pressure vessel 202) plays a major role in the expansion ratio of the foam. In some embodiments, the saturation pressure can range from 75 bar to 200 bar, preferably from 90 bar to 150 bar. The inert gas saturation temperature can range from 90°C to 200°C, depending on the dropping point and melting temperature of the particular biodegradable, industrially compostable, and / or recycled and / or recyclable polymer. Furthermore, the average pore size and cell density of the foam can be controlled to some extent by adjusting the saturation pressure, i.e., the pressure of inert gas saturation for the selected polymer. A high inert gas saturation pressure is ideal for achieving small average pore sizes and high cell densities.

[0072] In some embodiments, in a second stage after being saturated with the inert gas, the pellets of the masterbatch 204 are transferred to a hopper 206 configured to feed the pellets to an extruder 208. The pellets may be in an expanded state after being saturated with the inert gas. In some embodiments, the extruder 208 includes one or more extrusion screws 210 housed within a barrel 212 and configured to rotate. The rotation of the one or more extrusion screws 210 may be driven, for example, by a motor 214. In some embodiments, the one or more extrusion screws 210 are configured to convey, compress, and fuse the saturated pellets of the masterbatch 204 together as the pellets are extruded through the extruder 208 to form a polymer melt. In some embodiments, one or more biodegradable and / or recyclable binders are optionally included to aid in fusing the pellets together.

[0073] In some embodiments, the polymer melt is extruded by extruder 208 through die 216. In some embodiments, die 216 may be located at the end of extruder 208 and is configured to shape the polymer melt as it passes through die 216. In some embodiments, the temperature of die 216 is set at or just below the melting temperature of the polymer material. In some embodiments, the polymer melt is extruded through die 216 and passes through calibrator 218. In some embodiments, calibrator 218 is configured to cool the extrudate after extrusion through the die. In some embodiments, calibrator 218 is connected to temperature control unit 220 (e.g., a Thermolator® brand temperature control unit). In some embodiments, temperature control unit 220 is configured to control the temperature of calibrator 218. In some embodiments, calibrator 218 and / or temperature control unit 220 are configured to cool the extrudate sufficiently as it passes through calibrator 218 to solidify it.

[0074] In further embodiments, the calibrator 218 is connected to a vacuum system 222. In some embodiments, the vacuum system 222 is configured to create a low-pressure zone. As the polymer melt exits the die 216 and is exposed to the low-pressure zone, gases incorporated into the polymer melt expand and form an extruded foam 226. In further embodiments, a puller system 224 may be included to convey the extruded foam 226 away from the die 216. The puller system 224 may include, for example, one or more rollers configured to receive the extruded foam 226. In some embodiments, the rollers of the puller system aid in forming the extruded foam 226 (e.g., into a flat sheet).

[0075] FIG. 3 illustrates a system 300 for manufacturing flexible foam according to another non-limiting example. In some embodiments, the system 300 includes a hopper 302 configured to feed pellets of a masterbatch 304 to a first extruder 306. The pellets may be composed of any of the non-limiting thermoplastic polymer materials described above. In some embodiments, the first extruder 306 is a melt extruder. In some embodiments, the first extruder 306 includes one or more extrusion screws 308 housed within a barrel 310 and configured to rotate. Rotation of the one or more extrusion screws 308 may be driven, for example, by a first motor 312 connected to the extrusion screws 308 by a system of gears 314. In some embodiments, the one or more extrusion screws 308 are configured to convey, compress, and melt the pellets of the masterbatch 304 as they are extruded through the first extruder 306, forming a polymer melt.

[0076] System 300, in some embodiments, includes a supercritical fluid (SCF) input system 316 configured to supply an inert gas to first extruder 306 to be mixed with the polymer melt. In some such embodiments, SCF input system 316 includes, for example, one or more of a source (e.g., a tank) 318 of inert gas (e.g., nitrogen or carbon dioxide), a pump controller 320, valves 322, 324 for controlling the flow of the inert gas, and an injection line 326 for injecting the inert gas into first extruder 306. In some embodiments, SCF input system 316 is configured to introduce the inert gas into first extruder 306 as a supercritical fluid. In some such embodiments, SCF input system 316 is configured to inject the inert gas into first extruder 306 at a pressure and temperature above the critical point of the gas. For example, in some embodiments, SCF input system 316 is configured to introduce the supercritical fluid at a pressure ranging from about 150 bar to about 300 bar and a temperature ranging from about 150° C. to about 350° C. In some embodiments, SCF input system 316 is configured to introduce the supercritical fluid at a pressure ranging from about 90 bar to about 150 bar and a temperature ranging from about 90° C. to about 200° C. In some embodiments, the pressure and temperature within first extruder 306 are sufficient to maintain the inert gas in its supercritical state.

[0077] In some embodiments, the supercritical fluid and polymer melt are mixed in the first extruder 306 to form a single-phase solution. In some embodiments, the single-phase solution is extruded from the first extruder 306 to the second extruder 330 via a pipe 328. In some embodiments, the second extruder 330 is a cooled extruder. In some embodiments, the use of the second extruder 330 helps to avoid collapse and shrinkage of the foam cells. In further embodiments, the use of the second extruder 330 helps to produce a smooth, homogeneous foam structure. In some embodiments, the second extruder 330 includes one or more extrusion screws 332 housed within a second barrel 334 and configured to rotate. Rotation of the one or more extrusion screws 332 may be driven, for example, by a second motor 336 connected to the extrusion screws 332 by a second system gear 338. In some embodiments, the one or more extrusion screws 332 are internally cooled (e.g., via water, oil, or other coolant). In some such embodiments, cooling of the extrusion screw(s) 332 may prevent the polymeric material being extruded through the second extruder 330 from adhering to the extrusion screw(s) 332 .

[0078] In some embodiments, the second extruder 330 is configured to convey and extrude the polymer melt through the die 340. In some embodiments, the die 340 is configured to shape the polymer melt as it passes through the die 340. In some embodiments, the system 300 includes a mixer 342 disposed between the second extruder 330 and the die 340. In further embodiments, the system 300 includes a heat exchanger 344 disposed between the second extruder 330 and the die 340. In yet other embodiments, the system 300 includes a melt pump 346 disposed between the second extruder 330 and the die 340. In some embodiments, the melt pump 346 is configured to precisely control the output of the die 340. In some such embodiments, the melt pump 346 includes a suction side that receives the extruded material from the second extruder 330 and a discharge side that outputs the extruded material to the die 340. In some embodiments, the extruded material passes through the mixer 342 from the second extruder 330 to the melt pump 346. In some embodiments, melt pump 346 is configured to output extruded material at a more consistent pressure and volume to die 340. In some embodiments, heat exchanger 344 is configured to help regulate the temperature of second extruder 330, melt pump 346, and / or die 340. In some embodiments, as the polymer melt exits die 340, gases entrained in the polymer melt expand to form extruded foam 350. In some embodiments, a puller system 348 may be included to convey extruded foam 350 away from die 340.

[0079] In some embodiments, system 300 may further include one or more sensors 352 coupled to various components of the system. The one or more sensors 352 may include, for example, pressure sensors, temperature sensors, etc. configured to measure various operating parameters of the components. The one or more sensors 352 may be coupled, for example, to one or more of first extruder 306, second extruder 330, and die 340. In some embodiments, the one or more sensors 352 may be further configured to communicate (e.g., wirelessly) to a control system (not shown), which is configured to control operation of the components of system 300 in response to parameters detected by the one or more sensors 352. For example, the control system in some embodiments may rely on feedback from the one or more sensors 352 to operate and / or maintain certain components of system 300 within predetermined ranges of temperature and / or pressure. Extruder speed, temperature control system, and / or other components may be adjusted by the control system.

[0080] FIG. 4 illustrates a system 400 for manufacturing flexible foam according to a further non-limiting embodiment. In some embodiments, system 400 includes a hopper 402 configured to direct masterbatch pellets to a feeder 404. In some embodiments, feeder 404 is configured to supply the pellets to a mixer 406. Feeder 404 may be a loss-in-weight feeder in some embodiments. In some embodiments, feeder 404 is a gravimetric feeder that measures the weight of pellets to achieve and maintain a predetermined feed rate of the pellets to mixer 406. Mixer 406 may be configured as a first extruder, similar to first extruder 306 described for system 300 above. In some embodiments, mixer 406 includes a barrel containing one or more rotating screws configured to convey, compress, and / or melt pellets received from feeder 404, for example. The one or more screws may be driven by a motor. Mixer 406 may be, for example, a single screw melt extruder, or in other embodiments, a twin screw melt extruder.

[0081] As described in other embodiments above, the pellets of the masterbatch may be composed of any of the non-limiting thermoplastic polymer materials listed above. For example, the pellets may include or consist of one or more bio-based polymers (e.g., PBAT, biodegradable branched polyesters, or other aliphatic-aromatic polyesters). In other examples, the pellets may include or consist of one or more recyclable and / or recycled polymers (e.g., PEBA or other polyamides).

[0082] System 400, in some embodiments, includes a supercritical fluid (SCF) injection system 408 configured to deliver an inert gas to mixer 406 to mix with the pellets. In some such embodiments, SCF injection system 408 includes, for example, one or more sources (e.g., one or more tanks) of inert gas (e.g., nitrogen or carbon dioxide) and is configured to supply the inert gas to mixer 406. SCF injection system 408 can further include additional components including, for example, a pump controller, a valve for controlling the flow of the inert gas, and an injection line for injecting the inert gas into mixer 406. In some embodiments, SCF injection system 408 is configured to introduce the inert gas into mixer 406 as a supercritical fluid. In some such embodiments, SCF injection system 408 is configured to inject the inert gas into the first extruder at a predetermined pressure and temperature above the critical point of the gas. For example, in some embodiments, SCF injection system 408 is configured to introduce the supercritical fluid at a pressure ranging from about 150 bar to about 300 bar and a temperature ranging from about 150° C. to about 350° C. In some embodiments, SCF injection system 408 is configured to introduce the supercritical fluid at a pressure ranging from about 90 bar to about 150 bar and a temperature ranging from about 90° C. to about 200° C. In some embodiments, the pressure and temperature within mixer 406 are sufficient to maintain the inert gas in its supercritical state.

[0083] In some embodiments, the supercritical fluid and pellets are mixed in mixer 406. In some embodiments, the pellets are melted in mixer 406 and blended with a supercritical gas to form a single-phase solution. In some embodiments, the single-phase solution is fed from mixer 406 to extruder 410. Mixer 406 can be fluidly connected to extruder 410 using appropriate piping (not shown). In some embodiments, extruder 410 is a screw extruder including one or more extrusion screws housed within a barrel and configured to rotate. In some embodiments, extruder 410 can be configured similarly to extruder 330 described above in connection with system 300. In some embodiments, extruder 410 is a single-screw extruder. In other embodiments, extruder 410 may be a twin-screw extruder.

[0084] In some embodiments, extruder 410 is configured to convey and extrude a single-phase solution comprising a polymer melt and a supercritical fluid through die 412. In some embodiments, die 412 is configured to shape the polymer melt as it passes through die 412. Die 412, in some embodiments, is a flat sheet die sized and configured to shape the polymer melt into a flat sheet. In some embodiments, as the polymer melt exits die 412, gas entrained in the polymer melt expands to form an extruded foam sheet.

[0085] In some embodiments, system 400 optionally includes a roll calender 414 (e.g., a three-roll calender). The roll calender 414 can include multiple rollers, with the extruded foam sheet passing between pairs of rollers. In some embodiments, the use of the roll calender 414 can help smooth the surface of the extruded foam sheet as the sheet passes between the rollers. In further embodiments, system 400 may optionally include a flattening machine 416 configured to further flatten the extruded foam sheet. In some embodiments, system 400 may also include a thickness gauge 418 configured to measure the thickness of the extruded foam sheet. For example, thickness gauge 418 may be an automated tool that measures the thickness of the extruded foam sheet to determine whether the extruded foam sheet is within or outside a predetermined desired thickness range as part of a quality control process. Thickness gauge 418 can measure the thickness using, for example, visual analysis, a mechanical gauge (e.g., a caliper), an optical / laser thickness gauge, an ultrasonic thickness gauge, or other thickness gauge known in the art. System 400 may include other automated equipment useful for quality assurance, such as tools for determining the weight and / or density of the foam sheet and / or tools for surface characterization of the foam sheet (e.g., to determine whether the surface has a desired smoothness and / or to detect the presence of surface defects). In further embodiments, system 400 may optionally include a cutter 420 for cutting the extruded foam sheet to a desired size and / or a roller 422 configured to roll the extruded foam sheet into one or more rolls for subsequent packaging or use.

[0086] Autoclave Process Further embodiments of the present disclosure utilize an autoclave to produce flexible foams from the biodegradable and / or recyclable polymeric materials described herein. In some embodiments, the autoclave process may generally include introducing the polymeric material into an autoclave chamber, sealing the autoclave chamber, heating the autoclave chamber and pressurizing the autoclave chamber using an inert gas or supercritical fluid (e.g., N or CO), maintaining the pressure and temperature within the autoclave chamber for a time sufficient to impregnate the polymeric material and / or dissolve the inert gas or fluid in the polymeric material, and depressurizing the autoclave chamber by releasing the pressure to allow the inert gas or fluid to form expanding cell nuclei within the polymeric material and foam the polymeric material. The autoclave chamber may also be cooled during the depressurization step. The foamed polymeric material can then be removed from the autoclave chamber and, optionally, further shaped (e.g., by cutting, compressing, etc.) into a desired shape.

[0087] The polymeric material may comprise or consist of any one or more of the biodegradable and / or recyclable materials described in the above embodiments. For example, in some embodiments, the polymer is a bio-derived polymer (e.g., PBAT, a biodegradable branched polyester, or other aliphatic-aromatic polyester). In some embodiments, the polymer is a recyclable polymer (e.g., PEBA or other polyamide). In some embodiments, the polymer is a recyclable polymer that can be depolymerized to caprolactam monomer. As previously mentioned, the selected biodegradable and / or recyclable material may comprise or consist of one or more non-crosslinked polymers. In some embodiments, the polymeric material may be introduced into the autoclave in solid form, such as an extruded sheet or block of polymeric material. In other embodiments, the polymeric material may be dissolved in a suitable liquid solvent and introduced into the autoclave chamber as a solution.

[0088] Some non-limiting exemplary processes for forming flexible foam using an autoclave according to some embodiments are shown in the flowcharts of FIGS. 5 and 6. More specifically, FIG. 5 outlines one or more steps that may be included in a process 500 for forming flexible foam from a biodegradable and / or recyclable polymer. According to some embodiments, process 500 includes step 502, in which a masterbatch including or consisting of one or more biodegradable and / or recyclable polymers is dissolved in a solvent to form a liquid solution containing the dissolved polymer. The polymer may be selected from any of the thermoplastic polymers previously described herein (e.g., PEBA, polyamide, PBAT, biodegradable branched polyesters, or other aliphatic-aromatic polyesters), and the solvent may be a suitable organic solvent capable of dissolving the thermoplastic polymer. For example, the solvent may include methylene chloride or chloroform in some embodiments. Other solvents capable of dissolving thermoplastic polymers known in the art may also be utilized. The polymer is dissolved in a liquid solution, which can be introduced into the autoclave chamber in step 504 in a suitable container, for example, a material (e.g., glass, stainless steel, etc.) that can withstand the pressure and temperature of the autoclave and that does not react with the polymer or solvent. The container can have a size and shape selected based on the desired size and shape of the foam. After placing the liquid solution in the autoclave chamber, the autoclave chamber can be sealed.

[0089] In step 506, according to some embodiments, the autoclave chamber is heated to increase its internal pressure. In some embodiments, the autoclave chamber is pressurized with an inert gas, such as N or CO, pumped into the autoclave chamber from a gas supply. In some embodiments, the inert gas comprises or consists of CO. In some embodiments, the inert gas comprises or consists of N. In some embodiments, the temperature and pressure within the autoclave chamber are increased above the critical temperature and pressure of the inert gas (e.g., about 31° C. and about 7.4 MPa for CO). In some embodiments, the inert gas comprises or consists of both N and CO. In some embodiments, the inert gas comprises a mixture of 65%-85% CO and 35%-15% N by volume (e.g., 70% CO and 30% N, or 80% CO and 20% N). In some embodiments, the inert gas is converted to a supercritical fluid within the autoclave chamber. In some embodiments, the inert gas is introduced into the autoclave chamber already as a supercritical fluid (e.g., supercritical N or supercritical CO). In some embodiments, the inert gas or supercritical fluid is the only additive fluid used to pressurize the autoclave chamber. In other embodiments, the autoclave chamber may be further pressurized with air or a mixture of air and an inert gas. According to some embodiments, no water vapor is introduced into the autoclave chamber.

[0090] In step 508, according to some embodiments, the pressure and temperature within the autoclave chamber are maintained elevated for a sufficient time ("hold time") to allow the supercritical fluid within the autoclave chamber to diffuse and dissolve in the liquid solution. In some embodiments, the pressure and temperature within the autoclave chamber are not necessarily kept constant during this time, but are maintained within a desired range. In some embodiments, the hold time is a predetermined amount of time. The hold time can range, for example, from less than 1 minute to more than 30 minutes. In some embodiments, the hold time may be selected depending on factors such as the amount of liquid solution and the type of gas used. In some embodiments, the hold time can be more than 30 minutes, more than 60 minutes, at least 120 minutes, or at least 180 minutes, at least 240 minutes, at least 300 minutes, or at least 360 minutes, depending on the conditions. In other embodiments, the hold time may be less than 15 minutes, less than 10 minutes, or less than 5 minutes. In some embodiments, the hold time is 1 minute to 5 minutes, 1 minute to 10 minutes, 1 minute to 15 minutes, 1 minute to 30 minutes, or 1 minute to 60 minutes. In some embodiments, the retention time is between 60 minutes and 120 minutes. In some embodiments, the retention time is between 120 minutes and 180 minutes. In some embodiments, the retention time is between 180 minutes and 240 minutes. In some embodiments, the retention time is between 240 minutes and 300 minutes. In some embodiments, the retention time is between 300 minutes and 360 minutes.

[0091] Additional gas or supercritical fluid can be introduced into the autoclave chamber as needed to maintain the pressure in the autoclave chamber. In some embodiments, the autoclave can include one or more pressure and temperature sensors / gauges configured to sense or measure the pressure and temperature in the autoclave chamber. Such sensors / gauges can provide pressure and temperature data to a controller (e.g., a computer controller) configured to automatically adjust the supply of inert gas / supercritical fluid to maintain a desired pressure in the autoclave chamber. In some embodiments, for example, the controller is configured to maintain the pressure and / or temperature in the autoclave chamber at at least a predetermined target value (e.g., at least 31°C and at least 7.4 MPa when using CO2) during the hold time. In some embodiments, for example, the controller is configured to maintain the pressure and / or temperature in the autoclave chamber within ±10%, ±5%, or ±1% of the predetermined target value during the hold time. In some embodiments, the controller can control an exhaust valve configured to vent gas from the autoclave chamber to reduce the pressure in the autoclave chamber as needed. In some embodiments, the controller may also control a gas supply valve to allow additional gas or supercritical fluid to be introduced into the autoclave chamber to increase the pressure as needed. Additionally, in some embodiments, the controller may also be connected to a temperature control system configured to heat or cool the autoclave chamber in response to the sensed temperature to maintain the autoclave chamber within a desired temperature range. The temperature control system may include heating and / or cooling elements to regulate the temperature within the autoclave chamber.

[0092] A supercritical fluid (e.g., supercritical N or supercritical CO) acts as a foaming agent to foam the polymer, while, according to some embodiments, most of the solvent in the solution is vaporized and removed from the foam in the autoclave chamber. In some embodiments, when the autoclave chamber is pressurized with the supercritical fluid, the supercritical fluid dissolves and carries away the solvent, resulting in a homogeneous mixture of the polymer and the solvent / supercritical fluid mixture. According to some embodiments, once the solvent is removed from the solution, the polymer can solidify to form a flexible foam. When the pressure is released (step 510), the solvent / supercritical fluid mixture expands rapidly, foaming the polymer into a solid foam structure.

[0093] In some embodiments, the pressure is released after a predetermined hold time has elapsed. In some embodiments, the pressure can be released by venting gas from the autoclave chamber. For example, the controller can be programmed to open an exhaust valve to allow gas to exit the autoclave chamber, causing a pressure drop. In some embodiments, the pressure is reduced to approximately atmospheric pressure. The rate of pressure reduction can be controlled by the controller. In some embodiments, the pressure is reduced rapidly (e.g., less than 30 seconds, less than 10 seconds, less than 5 seconds, or less than 1 second). In other embodiments, the pressure is released more slowly (e.g., over 1 minute or more). In some embodiments, the pressure is released nearly instantly. In other embodiments, the pressure can be released in stages or gradually.

[0094] In some embodiments, when the pressure is released, the supercritical fluid dissolved in the solution forms cell nuclei (e.g., gas bubbles) in the polymer material. In some embodiments, the reduction in pressure causes the supercritical fluid to transition to a gaseous state, expanding the volume of the cell nuclei and foaming the polymer. In some embodiments, the solvent used to dissolve the polymer is dissolved by the supercritical fluid and can evaporate during the release of pressure. In some embodiments, the polymer can remove the solvent to form a solid foam structure. In some embodiments, the container used to hold the liquid solution imparts shape to the solid foam structure as the polymer comes out of solution and expands.

[0095] In some embodiments, a counter-pressure gas can be injected into the autoclave chamber to control the expansion of the foam. According to some embodiments, the counter-pressure gas can be injected in an amount sufficient to at least partially counteract the immediate expansion of the foam when the pressure in the autoclave chamber is released. In some embodiments, the use of a counter-pressure gas can help create a smoother surface on the foam, for example, by preventing air bubbles from penetrating the surface of the foam before the foam material solidifies. In some embodiments, the counter-pressure gas can include the same gas as the inert gas / supercritical fluid used to foam the polymeric material. For example, in some embodiments, when foaming a polymeric material using supercritical CO2, CO2 gas can be used as the counter-pressure gas, or when foaming a polymeric material using supercritical N2, N2 gas can be used as the counter-pressure gas. In other embodiments, a gas other than the supercritical fluid can be used as the counter-pressure gas. For example, when foaming a polymeric material using supercritical CO2, N2 gas or compressed air can be used as the counter-pressure gas in certain embodiments. In some embodiments, the dosing amount and pressure of the counter-pressure gas can be dynamically controlled based on the sensed pressure (e.g., via one or more pressure sensors) in the autoclave chamber. For example, in some embodiments, the controller used to maintain the desired pressure and / or temperature in the autoclave chamber may also be configured to control the amount of counter-pressure gas introduced into the autoclave chamber to counteract the expansion of the foam. The controller can receive data from one or more pressure sensors and determine the amount of counter-pressure gas based on these data.

[0096] In some embodiments, under certain conditions, such as relatively high temperatures and lower pressures, the supercritical fluid can expand the polymer to form an open-cell foam, where the cells are interconnected and have an open structure. Open-cell foams can be useful, for example, for applications requiring high surface area, high permeability, and breathability. Under other conditions, such as relatively low temperatures and higher pressures, the supercritical fluid can expand the polymer to form a closed-cell foam, where the cells are separated and have a closed structure. Closed-cell foams have low permeability and can be useful, for example, for applications such as impermeable shoe insoles and midsoles. Therefore, the cell structure of the foam can be tailored to the desired application using the selected autoclave conditions.

[0097] According to some embodiments, the foamed polymer material can be cooled (e.g., to room or ambient temperature) after or during pressure release. The cooling process can include passive heat dissipation from the autoclave chamber and / or active cooling via a temperature control system. In some embodiments, in step 512, the solidified foam can be removed from the autoclave chamber, washed to remove excess solvent remaining in the foam, and then dried. In some embodiments, the foamed sheet or block can have dimensions in the range of 2 to 3 times larger than the initial dimensions of the unfoamed polymer sheet or block (a 2x to 3x expansion ratio). Different polymers saturate differently with the inert supercritical fluid, resulting in different foam densities. In some embodiments, for example, the resulting foam density can be greater than 0.1 g / cm. 3 ~0.13g / cm 3 In some embodiments, the foam density ranges from 0.1 g / cm to 100 g / cm, depending on the intended end use of the foam. 3 ~0.28g / cm 3In some embodiments, a typical foam hardness can be in the range of 30 Asker C to 50 Asker C, e.g., between 35 Asker C and 45 Asker C. In some embodiments, in step 514, the foam may optionally be shaped (e.g., cut, compressed, rolled, etc. to a desired size / shape) for a desired purpose. For example, in some embodiments, the foam may be molded into a shoe component (e.g., a shoe insole or midsole). In other embodiments, the foam may be molded into a seat cushion or other foam product. Optionally, the foam may be subjected to a compression molding process. In some embodiments, for example, autoclaved foam is placed in a hot compression mold at a temperature range of about 120°C to about 200°C, e.g., 140°C to 160°C, for one to several minutes, and then cooled to about room temperature. This process slightly reduces the surface area of ​​the foam part and increases the density of the foam. As a non-limiting example, a foam part may have a 2x expansion ratio during the autoclave process, while compression molding can reduce the expansion ratio to 1.5x. The density of the foam can be increased by a compression molding process, and in some embodiments, the density is increased by about 12.5%.

[0098] FIG. 6 outlines one or more steps that may be included in a further process 600 for forming a flexible foam from a biodegradable and / or recyclable polymer according to some embodiments of the present disclosure. Process 600 may be similar to process 500, except that, in some aspects, the biodegradable and / or recyclable polymer is introduced into the autoclave chamber in solid form rather than dissolved in a solvent. For example, process 600, in some embodiments, includes step 602 of manufacturing or providing one or more sheets or blocks of biodegradable and / or recyclable polymer. In some embodiments, the sheets or blocks may be extruded sheets or blocks of polymer. In some such embodiments, the extruded polymer sheets or extruded polymer blocks may be formed by an extrusion process (e.g., process 100) as already described above. In some embodiments, the extruded polymer sheets or extruded polymer blocks are not foamed before being introduced into the autoclave chamber.

[0099] In some embodiments, a method according to the present disclosure includes a first extrusion process to produce a solid, unfoamed extruded polymer sheet or block, followed by an autoclave foaming process to expand the extruded polymer sheet or block into a foam. For example, in some embodiments, a system similar to system 200 (FIG. 2) may be used to first form an extruded polymer sheet or block, except that a pressure vessel 202 is not required to form the unfoamed extruded polymer. In this process, for example, pellets of masterbatch 204 are fed directly into hopper 206 without first being saturated with gas. Unsaturated pellets are fed by hopper 206 to extruder 208. In some embodiments, extruder 208 includes one or more extrusion screws 210 housed within barrel 212 and configured to rotate. Rotation of one or more extrusion screws 210 may be driven, for example, by motor 214. In some embodiments, one or more extrusion screws 210 are configured to convey, compress, and fuse saturated pellets of masterbatch 204 together as the pellets are extruded through extruder 208 to form a polymer melt. In some embodiments, the polymer melt is extruded by the extruder 208 through a die 216. In some embodiments, the die 216 may be located at the end of the extruder 208 and configured to shape the polymer melt as it passes through the die 216. In some embodiments, the temperature of the die 216 is set at or just below the melting temperature of the polymer material. In some embodiments, the polymer melt is extruded through the die 216 and passes through a calibrator 218. In some embodiments, the calibrator 218 is configured to cool the extrudate after extrusion through the die 216, as described in certain embodiments above. In some embodiments, a puller system 224 may be included to convey the extruded polymer away from the die 216. In this process, the extruded polymer does not foam as it exits the die 216 because the pellets are not pre-saturated with gas.The extruded polymer may then be shaped as desired, for example cut into blocks or rolled into sheets for later foaming / expansion in an autoclave process.

[0100] In some further embodiments, a system similar to system 300 (FIG. 3) may be used to initially form an extruded polymer sheet or block, except that SCF input system 316 is not required to form the non-foamed extruded polymer. In this process, for example, masterbatch pellets may be fed into hopper 302, which is configured to feed masterbatch 304 pellets to first extruder 306. The pellets may be composed of any of the non-limiting thermoplastic polymer materials described above. In some embodiments, first extruder 306 is a melt extruder. In some embodiments, first extruder 306 includes one or more extrusion screws 308 housed within barrel 310 and configured to rotate. Rotation of one or more extrusion screws 308 may be driven, for example, by a first motor 312 connected to extrusion screws 308 by a system of gears 314. In some embodiments, one or more extrusion screws 308 are configured to convey, compress, and melt the masterbatch 304 pellets as they are extruded through first extruder 306 to form a polymer melt. The polymer melt may then be conveyed to a second extruder 330 configured to convey and extrude the polymer melt through a die 340. In some embodiments, the die 340 is configured to shape the polymer melt as it passes through the die 340 to form the extruded polymer. In this process, no gas or supercritical fluid is mixed with the polymer, so the extruded polymer does not foam as it exits the die 340. The extruded polymer may then be cooled and shaped, for example, cut into blocks or rolled into sheets for later foaming / expansion in an autoclave process. In some examples, the extruded polymer block or sheet has a density of about 1.0 g / cm. 3 ~approx. 1.4g / cm3 , for example, about 1.1 g / cm 3 ~Approx. 1.3g / cm 3 The density may be

[0101] In further embodiments, a system similar to system 400 may be used to initially form an extruded polymer, except that SCF input system 408 is not required to form a non-foamed extruded polymer. In this process, according to some embodiments, pellets contained in hopper 402 are directed to feeder 404 (e.g., a loss-in-weight feeder), which then supplies the pellets to mixer 406. As described above, mixer 406 may be a melt extruder, for example, including a barrel containing one or more rotating screws configured to convey, compress, and melt pellets received from feeder 404 into a polymer melt. In mixer 406 according to these embodiments, SCF is not blended with the pellets. The polymer melt can then be supplied from mixer 406 to a further extruder 410. In some embodiments, extruder 410 is a screw extruder including one or more extrusion screws housed within a barrel and configured to rotate. In some embodiments, extruder 410 may be configured similarly to extruder 330 described above in connection with system 300. In some embodiments, extruder 410 is a single-screw extruder. In other embodiments, extruder 410 may be a twin-screw extruder. In some embodiments, extruder 410 is configured to convey and extrude a polymer melt through die 412. In some embodiments, die 412 is configured to shape the polymer melt as it passes through die 412. Die 412 is, in some embodiments, a flat sheet die sized and configured to shape the polymer melt into a flat extruded polymer sheet. Because SCF injection system 408 is omitted in these embodiments, the extruded polymer sheet is not foamed at this stage. In some examples, the extruded polymer sheet has a foam density of about 1.0 g / cm. 3 ~approx. 1.4g / cm 3 , for example, about 1.1 g / cm3 ~Approx. 1.3g / cm 3 The density may be

[0102] In some embodiments, the flat extruded polymer sheet may be fed to a roll calender 414 (e.g., a three-roll calender). The roll calender 414 may include multiple rollers, with the extruded polymer sheet passing between pairs of rollers. In some embodiments, the use of the roll calender 414 may help smooth the surface of the extruded polymer sheet as the sheet passes between the rollers. In still further embodiments, a flattening machine 416 is configured to further flatten the extruded polymer sheet. In some embodiments, a thickness gauge 418, as described above, may be used to measure the thickness of the extruded polymer sheet. In some embodiments, the extruded polymer sheet may then be cut (e.g., using a cutter 420) to a desired size for subsequent foaming / expansion in an autoclave process.

[0103] In further embodiments, the polymer sheet or block may be formed by a process other than extrusion. In some embodiments, the polymer sheet or block may be formed by an injection molding process. In some embodiments, an injection molding process can be used to provide a non-foamed polymer block or sheet having a desired preformed shape (also referred to herein as a "preformed sheet" or "preformed block") prior to autoclaving. In some such embodiments, the injection molding process uses a mold to impart a predetermined shape to the preformed sheet or preformed block. The preformed sheet or preformed block can have, for example, a shape similar to but smaller than the shape of the foamed product produced during the subsequent autoclave process. In some non-limiting embodiments, the preformed shape is not a rectangular prism and / or is not a polyhedron. In some embodiments, the preformed shape may be, for example, the shape of a shoe component (e.g., a shoe insole or midsole). The preformed shape may be any other shape that can be achieved by an injection molding process.

[0104] In some embodiments, the injection molding process for forming a preformed sheet or preformed block includes melting polymer pellets of a masterbatch to form a molten polymer and injecting the molten polymer into a mold that defines the size and shape of the preformed sheet or preformed block. For example, in some embodiments, the polymer pellets can be compressed and heated in a screw conveyor to form a molten polymer, which can then be injected (e.g., under screw pressure) into a mold having a predetermined shape and size to form the preformed sheet or preformed block. Then, according to some embodiments, the preformed sheet or preformed block can be cooled and solidified in the mold and then removed from the mold. In some embodiments, no foaming of the polymer material occurs during the injection molding process. The density of the preformed sheet or preformed block can be substantially the same as the density of the original polymer pellets. In some embodiments, for example, the preformed sheet or preformed block can have a density of about 1.0 g / cm. 3 ~approx. 1.4g / cm 3 , for example, about 1.1 g / cm 3 ~Approx. 1.3g / cm 3 The density of the granular material may be 0.015 to 0.015.

[0105] As described in other embodiments above, the pellets of the masterbatch may be composed of any of the non-limiting thermoplastic polymer materials listed above. For example, the pellets may include or consist of one or more bio-based polymers (e.g., PBAT, biodegradable branched polyesters, or other aliphatic-aromatic polyesters). In other examples, the pellets may include or consist of one or more recyclable and / or recycled polymers (e.g., PEBA or other polyamides). In some embodiments, the polymer pellets of the masterbatch do not include crosslinked polymers. In some embodiments, one or more additives described above may be optionally added to the polymer pellets and / or molten polymer during the injection molding process. The one or more additives may include, for example, one or more fillers, nucleating agents, colorants, UV stabilizers, and / or hydrolysis mitigators.

[0106] In some embodiments, the design of the mold for forming the preformed sheet or preformed block should take into account the expansion ratio of the final foamed product to be achieved during the subsequent autoclave process. This involves predicting how the thermoplastic polymer will expand and ensuring that the final foam structure has the desired density and mechanical properties. For example, the preformed sheet or preformed block may expand during autoclaving to dimensions that are approximately two to three times the initial dimensions of the preformed sheet or preformed block (a 2x to 3x expansion ratio). Thus, in this example, the mold may be designed to have predetermined dimensions that are one-half to one-third the dimensions of the finished foam sheet or foam block.

[0107] For example, some embodiments for manufacturing shoe midsoles include determining the dimensions of the desired finished shoe midsole and designing an injection mold to have proportionately smaller dimensions to account for subsequent expansion. For example, the mold may be shaped to have the shape of the finished midsole, but half to one-third the dimensions of the desired finished midsole. To illustrate, in one non-limiting example, to produce a US size 9 men's shoe size with final outer dimensions of approximately 11 inches (279.4 mm) long by 4 inches (101.6 mm) wide by 0.75 inches (19.05 mm) thick, the injection molding process may be configured to produce an unfoamed preformed midsole shape with outer dimensions of approximately 5.5 inches (139.7 mm) long by 2 inches (50.8 mm) wide by 0.375 inches (9.525 mm) thick. This example accounts for a minimum 2x expansion ratio from the preformed midsole shape to the final foamed midsole shape during the subsequent autoclave process. In some embodiments, the preformed shoe midsole has a thinner forefoot region and a thicker heel region. For example, a 15 mm forefoot and a 20 mm heel. The preformed shoe midsole shape may be any type of shoe shape and any type of shoe style. In some non-limiting examples, the preformed midsole shape may contain recessed areas or cavities for later addition of other types of shoe components therein or thereon. In some embodiments, stylized designs such as lines, shapes, or patterns may optionally decorate the preformed midsole shape. Furthermore, multiple holes may be added to the preformed midsole shape to improve adhesion to other shoe components in later stages of shoe assembly. All of the above-described decorations for the preformed midsole may be applied to a preformed mold in an injection molding process. FIG. 7 shows a comparison of the relative sizes of an unfoamed preformed block 702 of a shoe midsole shape before autoclaving and a foamed block 704 after autoclaving. The respective forefoot regions are designated as 702a and 704a, and the respective heel regions are designated as 702b and 704b.Preformed block 702 can have a width W1 and a length L1. Foam block 704 can have a width W2 that is greater than W1 and a length L2 that is greater than L1. In some embodiments, W2 is 2 to 3 times the value of W1. In some embodiments, L2 is 2 to 3 times the value of L1.

[0108] Referring again to FIG. 6 , in step 604, a polymer sheet or block, whether manufactured by one of the non-limiting processes described above or by some other method, is introduced into the autoclave chamber and the chamber is sealed. As described above, the polymer sheet or block may be formed by extrusion in some embodiments. In some embodiments, the polymer sheet or block may be injection molded. In some embodiments, the polymer sheet or block is a preformed sheet or preformed block having a preformed shape (e.g., the shape of a shoe component) as described above. In some embodiments, the polymer sheet or block may be placed on a rack or tray, which is then introduced into the autoclave chamber. Such racks or trays may be movable, for example, on wheels, tracks, or rails, to facilitate introduction into the autoclave chamber. In some embodiments, the polymer sheet or block is optionally suspended or hung within the autoclave chamber to maximize the exposed surface area of ​​the polymer sheet or block, which can, for example, facilitate saturation of the polymer sheet or block with the supercritical fluid during the autoclave process. In some embodiments, the polymer sheet or block may be suspended from a movable rack or tray.

[0109] In step 606, according to some embodiments, the autoclave chamber is heated to increase its internal pressure. In some embodiments, the autoclave chamber is pressurized with an inert gas, such as N, CO, or a mixture thereof, pumped into the autoclave chamber from a gas supply. In some embodiments, the inert gas comprises or consists of N. In some embodiments, the inert gas comprises or consists of CO. In some embodiments, the inert gas comprises or consists of both N and CO. In some embodiments, the inert gas comprises a mixture of 65%-85% CO and 35%-15% N by volume (e.g., 70% CO and 30% N, or 80% CO and 20% N). In some embodiments, the temperature and pressure within the autoclave chamber are elevated to at least the critical temperature and pressure of the inert gas (e.g., approximately 31° C. and 7.4 MPa for CO). Because the critical temperature and pressure of CO2 are greater than those of N2, when the inert gas is a mixture of N2 and CO2, the temperature and pressure must be increased to at least the critical temperature and pressure of CO2. In some embodiments, the pressure in the autoclave chamber is increased to at least 100 bar (10 MPa), at least 125 bar (12.5 MPa), at least 150 bar (15 MPa), at least 175 bar (17.5 MPa), or at least 200 bar (20 MPa). For example, the pressure in the autoclave chamber can be increased to about 180 bar (18 MPa) to about 200 bar (20 MPa). In some embodiments, the temperature in the autoclave chamber is increased to at least 75° C., at least 80° C., at least 85° C., at least 90° C., at least 95° C., at least 100° C., at least 105° C., at least 110° C., at least 115° C., at least 120° C., or at least 125° C. In some embodiments, for example, the temperature in the autoclave chamber is increased to about 95° C. to about 115° C. In some embodiments, the inert gas is converted to a supercritical fluid in the autoclave chamber.In some embodiments, the inert gas is introduced into the autoclave chamber already as a supercritical fluid (e.g., supercritical N or supercritical CO, or a mixture thereof). In some embodiments, the inert gas or supercritical fluid is the only additive fluid used to pressurize the autoclave chamber. In other embodiments, the autoclave chamber may be further pressurized with air or a mixture of air and an inert gas. According to some embodiments, no water vapor is introduced into the autoclave chamber.

[0110] In step 608, according to some embodiments, the pressure and temperature in the autoclave chamber are maintained elevated for a sufficient time ("hold time") to allow the polymer sheet or block to become saturated with the supercritical fluid in the autoclave chamber. In some embodiments, the pressure and temperature in the autoclave chamber are not necessarily kept constant during this time, but are maintained within a desired range. In some embodiments, the supercritical fluid is injected into the polymer sheet or block during this hold time. According to some embodiments, the hold time may be selected to be sufficient for the diffusion of the supercritical gas into the solid polymer sheet or block to reach equilibrium. In some embodiments, the hold time is a predetermined amount of time. The hold time can range from less than 1 minute to more than 30 minutes, depending on factors such as the size of the polymer sheet or block and the type of supercritical gas used. In some embodiments, the hold time can be greater than 30 minutes, greater than 60 minutes, at least 120 minutes, at least 180 minutes, at least 240 minutes, at least 300 minutes, or at least 360 minutes, depending on the conditions. In other embodiments, the retention time may be less than 15 minutes, less than 10 minutes, or less than 5 minutes. In some embodiments, the retention time is 1 to 5 minutes, 1 to 10 minutes, 1 to 15 minutes, 1 to 30 minutes, or 1 to 60 minutes. In some embodiments, the retention time is 60 to 120 minutes. In some embodiments, the retention time is 120 to 180 minutes. In some embodiments, the retention time is 180 to 240 minutes. In some embodiments, the retention time is 240 to 300 minutes. In some embodiments, the retention time is 300 to 360 minutes.

[0111] Similar to the previously described embodiment of process 500, additional gas or supercritical fluid can be introduced into the autoclave chamber as needed to maintain the pressure within the autoclave chamber. In some embodiments, the autoclave can include one or more pressure and temperature sensors / gauges configured to sense or measure the pressure and temperature within the autoclave chamber. Such sensors / gauges can provide pressure and temperature data to a controller (e.g., a computer controller) configured to automatically adjust the supply of inert gas / supercritical fluid to maintain the desired pressure within the autoclave chamber. In some embodiments, for example, the controller is configured to maintain the pressure and / or temperature within the autoclave chamber at at least a predetermined target value (e.g., a pressure within a range of about 180 bar (18 MPa) to about 200 bar (20 MPa) and a temperature within a range of about 95°C to about 115°C) during the hold time. In some embodiments, for example, the controller is configured to maintain the pressure and / or temperature within the autoclave chamber within ±10%, ±5%, or ±1% of the predetermined target value during the hold time. In some embodiments, the controller can control an exhaust valve configured to exhaust gas from the autoclave chamber to reduce the pressure in the autoclave chamber as needed. In some embodiments, the controller can also control a gas supply valve to allow additional gas or supercritical fluid to be introduced into the autoclave chamber to increase the pressure as needed. Further, in some embodiments, the controller can also be connected to a temperature control system configured to heat or cool the autoclave chamber in response to the sensed temperature to maintain the autoclave chamber within a desired temperature range. The temperature control system can include heating and / or cooling elements to adjust the temperature in the autoclave chamber.

[0112] In some embodiments, the pressure is released after a predetermined hold time has elapsed in step 610. In some embodiments, the pressure can be released by venting gas from the autoclave chamber. For example, the controller can be programmed to open an exhaust valve to allow gas to exit the autoclave chamber, causing a pressure drop. In some embodiments, the pressure is reduced to approximately atmospheric pressure. The rate of pressure reduction can be controlled by the controller. In some embodiments, the pressure is reduced rapidly (e.g., in less than 30 seconds, less than 10 seconds, less than 5 seconds, or less than 1 second). In other embodiments, the pressure is released more slowly (e.g., over a period of 1 minute or more). In some embodiments, the pressure is released nearly instantaneously. In other embodiments, the pressure can be released in stages or gradually.

[0113] In some embodiments, when the pressure is released, the supercritical fluid injected into the polymer sheet or block forms numerous cellular nuclei (e.g., gas bubbles) in the polymer material. In some embodiments, the reduction in pressure causes the supercritical fluid to transition to a gaseous state, expanding the volume of the cellular nuclei and foaming the polymer sheet or block.

[0114] In some embodiments, a counter-pressure gas can be injected into the autoclave chamber to control the expansion of the foam. According to some embodiments, the counter-pressure gas can be injected in an amount sufficient to at least partially counteract the immediate expansion of the foam when the pressure in the autoclave chamber is released. In some embodiments, the use of a counter-pressure gas can help create a smoother surface on the foam, for example, by preventing air bubbles from penetrating the surface of the foam. In some embodiments, the counter-pressure gas can include the same gas as the inert gas / supercritical fluid used to foam the polymeric material. For example, in some embodiments, when foaming a polymeric material using supercritical CO2, CO2 gas can be used as the counter-pressure gas, or when foaming a polymeric material using supercritical N2, N2 gas can be used as the counter-pressure gas. In other embodiments, a gas other than the supercritical fluid is used as the counter-pressure gas. For example, when foaming a polymeric material using supercritical CO2, N2 gas or compressed air can be used as the counter-pressure gas in certain embodiments. In some embodiments, the dosing amount and pressure of the counter-pressure gas can be dynamically controlled based on the sensed pressure (e.g., via one or more pressure sensors) in the autoclave chamber. For example, in some embodiments, the controller used to maintain the desired pressure and / or temperature in the autoclave chamber may also be configured to control the amount of counter-pressure gas introduced into the autoclave chamber to counteract the expansion of the foam. The controller can receive data from one or more pressure sensors and determine the amount of counter-pressure gas based on these data.

[0115] In some embodiments, under certain conditions, such as relatively high temperatures and lower pressures, the supercritical fluid can expand the polymer to form an open-cell foam, where the cells are interconnected and have an open structure. Open-cell foams can be useful, for example, for applications requiring high surface area, high permeability, and breathability. Under other conditions, such as relatively low temperatures and higher pressures, the supercritical fluid can expand the polymer to form a closed-cell foam, where the cells are separated and have a closed structure. Closed-cell foams have low permeability and can be useful, for example, for applications such as impermeable shoe insoles and midsoles. Therefore, the cell structure of the foam can be tailored to the desired application using the selected autoclave conditions.

[0116] According to some embodiments, the foamed polymer sheet or block can be cooled (e.g., to room temperature) after or during pressure release. The cooling process can include passive heat dissipation from the autoclave chamber and / or active cooling via a temperature control system. In some embodiments, the foamed sheet or block can be removed from the autoclave chamber in step 612. In some embodiments, the foamed sheet or block can have dimensions in the range of 2-3 times larger than the initial dimensions of the unfoamed polymer sheet or block (a 2-3 times expansion ratio). Different polymers saturate differently with the inert supercritical fluid, resulting in different foam densities. In some embodiments, for example, the resulting foam density can be greater than 0.1 g / cm. 3 ~0.13g / cm 3 In some embodiments, the foam density ranges from 0.1 g / cm to 100 g / cm, depending on the intended end use of the foam. 3 ~0.28g / cm 3 In some embodiments, a typical foam hardness may be in the range of 30 Asker C to 50 Asker C, for example, between 35 Asker C and 45 Asker C.

[0117] In some embodiments, in step 614, the foam sheet or block may optionally be shaped (e.g., cut, compressed, rolled to a desired size / shape, etc.) for a desired purpose. For example, in some embodiments, the foam may be molded into a shoe component (e.g., a shoe insole or midsole). In other embodiments, the foam may be molded into a seat cushion or other foam product. In some embodiments, if a preformed sheet or preformed block is utilized, the foam may already have a shape that closely matches the desired shape of the finished foam product. Nevertheless, the foam may still be subjected to buffing, deburring, sanding, or other surface finishing processes, as needed. Optionally, the foam may be subjected to a compression molding process. In some embodiments, for example, autoclaved foam is placed in a hot compression mold at a temperature range of about 120°C to about 200°C, e.g., 140°C to 160°C, for one to several minutes, and then cooled to about room temperature. This process slightly reduces the surface area of ​​the foam part and increases the density of the foam. As a non-limiting example, a foam part may have an expansion ratio of 2x during the autoclave process, and compression molding can reduce the expansion ratio to 1.5x. The density of the foam can be increased by the compression molding process, and in some embodiments, the density can be increased by about 12.5%.

[0118] In some embodiments, the autoclave chamber may be large enough to accommodate several polymer sheets or blocks simultaneously. For example, the autoclave chamber may include a series of shelves or racks for placing separate polymer sheets or blocks that can be expanded simultaneously in a single process. FIG. 8 is a simplified diagram illustrating an autoclave system 800 that can be used to produce foams according to embodiments described herein, e.g., in processes 500 and / or 600. In some embodiments, the autoclave system 800 includes an autoclave 802 having an interior autoclave chamber 804 that can be closed or opened by an autoclave door 806. One or more racks 808 may be positioned within the autoclave chamber 804 to hold one or more polymer sheets or blocks 900. The racks 808 should be sufficiently spaced to accommodate the expansion of the polymer sheets or blocks 900. Furthermore, in some embodiments, the racks 808 may be movable relative to the autoclave 802, e.g., into and out of the autoclave chamber 804 to facilitate the introduction of the polymer sheets or blocks 900 into the autoclave chamber 804. In some embodiments, the polymer sheet or block 900 is formed by an extrusion process, for example, as described in any of the previous embodiments. In some embodiments, the polymer sheet or block may include or consist of one or more preformed sheets or preformed blocks 902. As described in the previous embodiments, the preformed sheet or preformed block 902 can have a preformed shape similar to, but smaller than, the desired finished foam product. For example, in some embodiments, the preformed sheet or preformed block 902 may be shaped like a shoe component, as shown, for example, as preformed block 702 in FIG. 7. In some embodiments, the preformed sheet or preformed block 902 is formed by injection molding, as described above.In some embodiments, the preformed sheet or preformed block 902 is suspended from a rack 808. In some embodiments, suspending the preformed sheet or preformed block 902 can increase the amount of exposed surface area and facilitate saturation with the supercritical fluid. The polymer sheet or block 900, including the preformed sheet or preformed block 902, can include or be composed of any of the recyclable, biodegradable, and / or compostable thermoplastic polymers described above (e.g., PEBA, polyamide, PBAT, biodegradable branched polyester, or other aliphatic-aromatic polyesters). In some embodiments, the polymer sheet or block 900, including the preformed sheet or preformed block 902, does not include a cross-linked polymer.

[0119] In some embodiments, autoclave system 800 further includes one or more gas sources 810. Gas source 810 is configured to supply an inert gas to the autoclave chamber, for example, via gas supply line 812. As discussed, the inert gas, according to some embodiments, may include nitrogen gas, carbon dioxide, or a mixture thereof. When the inert gas includes a mixture of different gases, each gas may be supplied via a separate gas source 810. Each gas source 810 may include, for example, one or more pressurized gas cylinders or other gas sources used in the art. Gas source 810 and / or gas supply line 812 may include a valve 814 configured to control the input of inert gas from gas source 810 to autoclave chamber 804. In some embodiments, a controller 820 is used to control the opening and closing of valve 814.

[0120] In further embodiments, autoclave system 800 includes at least one exhaust line 816 configured to allow gases to exit autoclave chamber 804. In some embodiments, pressure within autoclave chamber 804 can be reduced by venting gases through exhaust line 816. In some embodiments, exhaust line 816 can be opened and closed via exhaust valve 818. In some embodiments, operation of exhaust valve 818 may also be controlled by controller 820. Although not shown, in some embodiments, exhaust line 816 may be connected to a gas collection / recycle system to capture gases vented from autoclave chamber 804.

[0121] In some embodiments, autoclave system 800 includes at least one heating element 826 configured to heat the temperature within autoclave chamber 804 during the autoclave process. Heating element 826 may include, for example, a heating coil or other heat source used in the art suitable for achieving a desired temperature range (e.g., about 95°C to about 115°C). In some embodiments, at least one heating element 826 may be controlled by controller 820. In further embodiments, autoclave system 800 may also include a cooling system (not shown) configured to reduce the temperature of autoclave chamber 804. The cooling system may include, for example, a water heat exchanger or a cooling jacket.

[0122] Controller 820, in some embodiments, is a computer controller configured to control the operation of one or more elements of autoclave system 800. As described, controller 820 can be configured to control the operation of gas valve 814, exhaust valve 818, and / or heating element 826 to adjust and / or maintain the pressure, temperature, and hold time within autoclave chamber 804 during the autoclave foam process. In some embodiments, controller 820 controls the operation of these functions in response to receiving at least autoclave chamber temperature and pressure data. Such data can be determined by one or more temperature sensors 822 and one or more pressure sensors 824. In some embodiments, one or more temperature sensors 822 and one or more pressure sensors 824 are configured to provide real-time or near-real-time temperature and pressure data to controller 820. In some embodiments, one or more temperature sensors 822 and one or more pressure sensors 824 are configured to provide data to controller 820 at regular intervals (e.g., once per minute). In some embodiments, the temperature and pressure data can be compared to preset target values ​​(e.g., by a computer processor in controller 820), and if the sensed data deviates from the target values ​​by more than a predetermined amount, controller 820 causes activation of one or more of gas valve 814, exhaust valve 818, and / or heating element 826. For example, if the sensed pressure in autoclave chamber 804 is lower than a preset target pressure range, controller 820 can open gas valve 814 to supply more gas into autoclave chamber 804 to increase the pressure. If the sensed pressure in autoclave chamber 804 is higher than the preset target pressure range, controller 820 can open exhaust valve 818 to allow gas to exit autoclave chamber 804 via exhaust line 816. Similarly, controller 820 can be configured to activate heating element 826 if the sensed temperature is lower than the current target temperature.

[0123] In other embodiments, the autoclave chamber can be sized so that a single foam sheet or block substantially fills the entire autoclave chamber as the cell core expands. In some such embodiments, the autoclave chamber can act as a mold cavity, such that the walls of the autoclave chamber impart a desired shape and / or size to the foam sheet or block as it expands to fill the autoclave chamber.

[0124] In some embodiments, the methods of the present disclosure generally include placing a solid polymer sheet or block into a high-pressure resistant mold cavity, closing and sealing the mold cavity, heating the mold cavity (e.g., to about 100°C to about 160°C), introducing a supercritical fluid (e.g., supercritical N2 or supercritical CO2) into the mold cavity, rapidly diffusing the supercritical fluid into the solid polymer sheet or block at high temperature and pressure (e.g., about 90 bar to about 200 bar), and, after a sufficient holding time for the supercritical fluid, rapidly (e.g., instantaneously) releasing the pressure of the supercritical fluid in the mold cavity such that the solid polymer sheet or block in the mold cavity expands and grows until it substantially fills the mold cavity volume.

[0125] In some embodiments, heating the mold cavity includes heating the mold cavity to a predetermined temperature. The predetermined temperature may be, for example, higher than the critical temperature of the supercritical fluid. In some embodiments, the high pressure in the mold cavity is achieved by pressurizing the mold cavity with a sufficient amount of supercritical fluid to reach a desired pressure. The desired pressure may be, for example, greater than the critical pressure of the supercritical fluid. In some embodiments, the mold cavity can be rapidly opened to allow the foam sheet or block to continue expanding outside the mold cavity. In still further embodiments, the mold cavity can be cooled (e.g., to about 90°C to about 130°C) immediately before or simultaneously with the release of the supercritical fluid pressure.

[0126] In some embodiments, the mold cavity is configured as an autoclave chamber, e.g., as described above. In some embodiments, the mold cavity is formed between an upper mold and a lower mold, and can be clamped together (e.g., via hydraulic or pneumatic clamping) and quickly unclamped open after placement of a solid polymer sheet or block. In some such embodiments, one or both of the upper and lower molds may be provided with at least one inlet valve for introducing supercritical fluid and at least one exhaust valve for rapidly and instantaneously releasing the supercritical fluid from the mold cavity.

[0127] According to some embodiments, the holding time may be selected to be sufficient for the diffusion of the supercritical gas into the solid polymer sheet or block to reach equilibrium. For example, the holding time may range from less than 1 minute to more than 30 minutes, depending on factors such as the size of the polymer sheet or block and the type of supercritical gas used. In some embodiments, the holding time may be greater than 30 minutes, greater than 60 minutes, at least 120 minutes, at least 180 minutes, at least 240 minutes, at least 300 minutes, or at least 360 minutes, depending on the conditions. In other embodiments, the holding time may be less than 15 minutes, less than 10 minutes, or less than 5 minutes. In some embodiments, the holding time is between 1 minute and 5 minutes, between 1 minute and 10 minutes, between 1 minute and 15 minutes, between 1 minute and 30 minutes, or between 1 minute and 60 minutes. In some embodiments, the holding time is between 60 minutes and 120 minutes. In some embodiments, the holding time is between 120 minutes and 180 minutes. In some embodiments, the holding time is between 180 minutes and 240 minutes. In some embodiments, the holding time is between 240 minutes and 300 minutes. In some embodiments, the retention time is between 300 minutes and 360 minutes.

[0128] As with other embodiments, the initial solid polymer sheet or block may be formed by extrusion, injection molding, or other processes described herein and may be formed from any of the recyclable, biodegradable, and / or compostable thermoplastic polymers described above (e.g., PEBA, polyamide, PBAT, biodegradable branched polyesters, or other aliphatic-aromatic polyesters). The polymer sheet or block is preferably non-crosslinked and, according to some embodiments, remains non-crosslinked throughout the foaming process. The size of the initial solid polymer sheet or block may be selected, for example, so that the mold cavity has a volume that is about 1.1 to about 5 times the volume of the initial solid polymer sheet or block. According to some embodiments, the solid polymer sheet or block can be expanded to fill substantially the entire volume of the mold cavity, for example, so that the expanded foam has a volume within the mold cavity that is about 1.1 to about 5 times the volume of the initial solid polymer sheet or block. In some embodiments, the foam can continue to expand outside the mold cavity after being ejected from the mold cavity. In such embodiments, the expanded foam may achieve a final volume greater than the volume of the mold cavity before cutting and shaping. In some embodiments, the expanded foam may be formed into a desired shape by the mold cavity. In some embodiments, the foam may be further cut or shaped as needed after being removed from the mold cavity.

[0129] As described herein, foams produced according to embodiments of the present disclosure may be useful in a variety of industries and end products, including, but not limited to, footwear components (e.g., shoe insoles or midsoles), seating components, protective gear components, vehicle components, bedding materials, and watersports accessories. In some embodiments, extruded foams of the present disclosure may be formed in a variety of predetermined dimensions (e.g., thickness, length, width) depending on the intended use. In further embodiments, the foam can then be cut or shaped (e.g., by compression molding) to form foam pieces useful for producing end products. For example, sheets of biodegradable and / or recyclable foam produced according to embodiments of the present disclosure can be die-cut into usable parts, which may be called "blockers." The blockers can then be compression molded to form, for example, contoured footwear midsoles for use in assembling shoes or other footwear.

[0130] Because foams according to certain embodiments are produced from recycled, recyclable, biodegradable, and / or compostable materials without crosslinking, the foams offer an environmentally friendly alternative to traditional foam materials (e.g., EVA or TPU foams). At the end of the foam's useful life, the foam can optionally be biodegraded or composted, in the case of biodegradable foams, or recycled and reprocessed (e.g., into new foam), in the case of recyclable foams. In some embodiments, the absence of crosslinkers or other inhibiting chemical additives allows the foam to be depolymerized back to its usable precursor components (e.g., monomers).

[0131] It should be understood that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the present invention, as defined by the appended claims. It should also be apparent that individual elements identified herein as belonging to a particular embodiment may be included in other embodiments of the present invention. Moreover, the scope of this application is not intended to be limited to the particular embodiments of the process, machine, manufacture, and compositions of matter, means, methods, and steps described herein. As one skilled in the art will readily appreciate from this disclosure, any currently existing or later-developed process, machine, manufacture, composition of matter, means, method, or step that performs substantially the same function or achieves substantially the same result as the corresponding embodiment described in this disclosure can be utilized in accordance with the present invention.

Claims

1. 1. A process for producing a foam, the process comprising: introducing a polymer sheet or block into an autoclave chamber, said polymer sheet or block comprising one or more non-crosslinked thermoplastic polymers that are recyclable and / or biodegradable; pressurizing the autoclave chamber to a high pressure using a supercritical fluid; maintaining the elevated pressure in the autoclave chamber for a time sufficient to infuse the supercritical fluid into the polymer sheet or block; reducing the pressure in the autoclave chamber to allow the injected supercritical fluid to form cell nuclei throughout the polymer sheet or block; and expanding said cellular cores to form a foam from said polymer sheet or block in said autoclave chamber.

2. 10. The process of claim 1, further comprising manufacturing the polymer sheet or block by an extrusion process prior to introducing the polymer sheet or block into the autoclave chamber.

3. The extrusion process comprises: feeding pellets of said one or more non-crosslinked thermoplastic polymers into an extruder; compressing and melting the pellets in the extruder to form a polymer melt; and extruding the polymer melt through a die.

4. The extrusion process comprises: cooling the polymer melt after it exits the die to form a solid polymer extrudate; 4. The process of claim 3, further comprising cutting the solid polymer extrudate to form the polymer sheet or block.

5. 5. The process of claim 4, wherein the extrusion process further comprises passing the solid polymer extrudate between rollers to flatten the solid polymer extrudate before cutting it.

6. 10. The process of claim 1, further comprising manufacturing the polymer sheet or block by an injection molding process prior to introducing the polymer sheet or block into the autoclave chamber.

7. The injection molding process comprises: forming a molten polymer from pellets of said one or more non-crosslinked thermoplastic polymers; injecting the molten polymer into a mold having a predetermined shape and size; and cooling the molten polymer to solidify the polymer into the polymer sheet or block having the shape and size of the mold.

8. 8. The process of claim 7, wherein the foam has dimensions that are 2 to 3 times the dimensions of the size of the mold.

9. The process of claim 7 wherein the predetermined shape of the mold is the shape of a shoe component.

10. The process of claim 9 , wherein the shoe component is a shoe midsole.

11. 10. The process of claim 1, wherein pressurizing the autoclave chamber to the elevated pressure using a supercritical fluid comprises introducing a sufficient amount of the supercritical fluid into the autoclave chamber to obtain the elevated pressure.

12. 10. The process of claim 1, wherein pressurizing the autoclave chamber to the elevated pressure using a supercritical fluid comprises introducing an inert gas into the autoclave chamber and converting the inert gas into a supercritical fluid within the autoclave chamber.

13. 1. A process for producing a foam, the process comprising: placing a polymer sheet or block into a mold cavity, the polymer sheet or block comprising one or more non-crosslinked thermoplastic polymers that are recyclable and / or biodegradable; closing and sealing the mold cavity; heating the mold cavity to a predetermined temperature; introducing a sufficient amount of supercritical fluid into the mold cavity to pressurize the mold cavity; allowing the supercritical fluid to diffuse into the polymer sheet or block for a predetermined amount of time; after the predetermined amount of time, releasing the pressure in the mold cavity to allow the polymer sheet or block to expand within the mold cavity. process.

14. 14. The process of claim 13, wherein the polymer sheet or block expands to substantially fill the mold cavity.

15. 14. The process of claim 13, wherein the predetermined amount of time is sufficient for the diffusion of the supercritical gas into the solid polymer sheet or block to reach equilibrium.

16. 14. The process of claim 13, wherein the predetermined temperature is greater than the critical temperature of the supercritical gas.

17. 14. The process of claim 13, wherein the polymer sheet or block is an extruded polymer sheet or block.

18. 14. The process of claim 13, further comprising manufacturing the polymer sheet or block by an extrusion or injection molding process prior to placing the polymer sheet or block in the mold cavity.

19. 14. The process of claim 13, further comprising cooling the mold cavity prior to or simultaneously with releasing the pressure in the mold cavity.

20. The supercritical fluid is supercritical CO ２ , supercritical N ２ or a mixture thereof.

21. The supercritical fluid is supercritical N ２ The process according to any one of claims 1 to 19, wherein

22. The process of any one of claims 1 to 21, wherein the one or more non-crosslinked thermoplastic polymers comprise a polyamide or polyamide copolymer.

23. 22. The process of any one of claims 1 to 21, wherein the one or more non-crosslinked thermoplastic polymers comprise a polymer selected from the group consisting of polyether block amide (PEBA), polyamide 6, polyamide 6 / 6-6, polyamide 12, or a blend comprising one or more thereof.

24. The one or more non-crosslinked thermoplastic polymers may be selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), poly(L-lactic acid) (PLLA), poly(butylene adipate-co-terephthalate) (PBAT), polycaprolactone (PCL), polyhydroxy alkanoate (PHA), polyhydroxybutyrate (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate (PBA), thermoplastic starch (TPS), and the like.

22. The process of any one of claims 1 to 21, comprising a polymer selected from the group consisting of: starch, and blends comprising one or more thereof.

25. The process of any one of claims 1 to 21, wherein the one or more non-crosslinked thermoplastic polymers comprise poly(butylene adipate-co-terephthalate) (PBAT).

26. The process of any one of claims 1 to 21, wherein the one or more non-crosslinked thermoplastic polymers consist of poly(butylene adipate-co-terephthalate) (PBAT).

27. The process of any one of claims 1 to 21, wherein the one or more non-crosslinked thermoplastic polymers comprise a bio-based polymer.

28. The process of any one of claims 1 to 21, wherein the one or more non-crosslinked thermoplastic polymers comprise a branched polyester.

29. The one or more non-crosslinked thermoplastic polymers may be selected from the group consisting of poly(1,4-butylene adipate-co-1,4-butylene terephthalate), poly(1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene terephthalate), poly(1,4-butylene brassylate-co-1,4-butylene terephthalate), poly(1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene azelate-co-1,4-butylene terephthalate), poly(1,4-butylene succinate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene adipate-co-1,4-butylene succinate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate nate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate- co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate), poly(1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene brassylate-co-1,4-butylene sebacate-co-1,4-butylene terephthalate), and poly(1,The process of any one of claims 1 to 21, comprising one or more aliphatic-aromatic polyesters selected from the group consisting of 1,4-butylene azelate-co-1,4-butylene succinate-co-1,4-butylene adipate-co-1,4-butylene sebacate-co-1,4-butylene brassylate-co-1,4-butylene terephthalate.

30. The process of any one of claims 1 to 21, wherein the one or more non-crosslinked thermoplastic polymers comprise one or more polymers derived from recycled feedstocks.

31. A foam produced by the process of any one of claims 1 to 30.

32. 32. The foam of claim 31 , wherein the foam is recyclable, biodegradable, and / or industrially compostable.

33. 32. The foam of claim 31, which is free of crosslinking agents.

34. 31. An article comprising a foam produced by the process of any one of claims 1 to 30, wherein the article is a footwear component, a seating component, a protective gear component, a vehicle component, bedding, or a water sports accessory.

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