Thermoplastic foam composition comprising biomass-based carbon-containing particulate material

Abstract

A thermoplastic foam composition for low density and high stiffness articles includes a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam. The thermoplastic foam composition has a core density of between 12 g / liter and 400 g / liter as measured according to ASTM-D3575-W Test Method A. The thermoplastic foam composition is characterized in that the thermoplastic foam composition has a core density of between 12 g / liter and 400 g / liter. The thermoplastic foam composition also has an elastic modulus of between 60 lbs / sq. Inch and 3500 lbs / sq. Inch as measured according to ASTM-C203 Method I, Equation 13.

Description

Technical Field

[0001] The present invention generally relates to thermoplastic foam compositions comprising biomass-based carbonaceous particulate materials. Background Art

[0002] Foam compositions often include polymer foam and additives encapsulated in the polymer foam. One additive often encapsulated in polymer foam is carbon black. Carbon black is a colorant that provides color to polymer foam and is an ultraviolet (UV) stabilizer that protects polymer foam from degradation due to exposure to ultraviolet energy. However, carbon black is a petroleum-based additive produced by the reaction of hydrocarbon fuels with air at high temperatures and is therefore non-renewable and unsustainable, has a high global warming potential (GWP), and leaves a large carbon footprint.

[0003] Therefore, there remains a need to provide improved foam compositions. Summary of the invention

[0004] The present invention provides a thermoplastic foam composition for low density and high stiffness articles. The thermoplastic foam composition comprises a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam. The thermoplastic foam composition has a core density between 12 g / L and 400 g / L measured according to ASTM-D3575-W Test Method A. The thermoplastic foam composition has an elastic modulus between 60 psi and 3500 psi measured according to ASTM-C203 Method I, Equation 13.

[0005] The present invention also provides a thermoplastic polyurethane foam composition for low-density and high-rigidity products. The thermoplastic polyurethane foam composition comprises a thermoplastic polyurethane foam and a biomass-based carbonaceous particulate material encapsulated in the thermoplastic polyurethane foam. The thermoplastic polyurethane foam composition has a core density between 12 g / L and 400 g / L measured according to ASTM-D3575-W Test Method A. The thermoplastic polyurethane foam composition has an elastic modulus between 60 psi and 700 psi measured according to ASTM-C203 Method I, Equation 13.

[0006] Unactivated biomass-based carbon-containing granular materials and biomass-based carbon-containing granular materials are non-petroleum-based additives, are renewable resources and are sustainable, have low global warming potential (GWP), and leave a low carbon footprint. More specifically, unactivated biomass-based carbon-containing granular materials and biomass-based carbon-containing granular materials have a low carbon footprint because the biomass from which the unactivated biomass-based carbon-containing granular materials and biomass-based carbon-containing granular materials are derived sequesters carbon dioxide from the atmosphere during its life. In addition, unactivated biomass-based carbon-containing granular materials and biomass-based carbon-containing granular materials are suitable for encapsulation in foam to provide low-density products, while also adjusting the elastic modulus of the foam to provide high-rigidity products.

[0007] Therefore, certain features of embodiments of the present invention are outlined so that their detailed description may be better understood, and so that the contribution of the present invention to the art may be better appreciated. Other or optional features of embodiments of the present invention will be described in more detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Other advantages of the present invention will be readily appreciated as will become better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings, in which:

[0009] Figure 1 is a scanning electron microscope image of a thermoplastic foam composition comprising a thermoplastic foam and a biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam;

[0010] Figure 2 yes Figure 1 A scanning electron microscope image of a thermoplastic foam composition at a higher resolution; and

[0011] Figure 3 yes Figure 1 and Figure 2 Scanning electron microscope image of a thermoplastic foam composition at higher resolution. DETAILED DESCRIPTION

[0012] With reference to the accompanying drawings, a thermoplastic foam composition for low density and high stiffness articles is provided. The thermoplastic foam composition comprises a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam. The thermoplastic foam composition has a core density between 12 g / L and 400 g / L measured according to ASTM-D3575-W Test Method A. The thermoplastic foam composition has an elastic modulus between 60 psi and 3500 psi measured according to ASTM-C203 Method I, Equation 13.

[0013] Unactivated biomass-based carbonaceous granular materials are non-petroleum-based additives, are renewable resources and sustainable, have low global warming potential (GWP), and leave a low carbon footprint. More specifically, unactivated biomass-based carbonaceous granular materials have a low carbon footprint because the biomass from which the unactivated biomass-based carbonaceous granular materials are derived sequesters carbon dioxide from the atmosphere during its life. In addition, unactivated biomass-based carbonaceous granular materials are suitable for encapsulation in thermoplastic foams to provide low-density products, while also adjusting the elastic modulus of the thermoplastic foam to provide high-rigidity products. Unactivated biomass-based carbonaceous granular materials can be a colorant that provides color to thermoplastic foams, and are a UV (UV) stabilizer that prevents thermoplastic foams from being degraded by exposure to UV energy.

[0014] Unactivated biomass-based carbonaceous particulate materials are derived from biomass feedstocks that have undergone pyrolysis, including, but not limited to, wood materials (e.g., wood, wood chips and / or leaves) from coniferous and / or deciduous trees, including maple trees, more specifically, rock maple (acer psuedoplatanus) trees, including their wood, wood chips and / or leaves, which are some of the most common maple leaves in Europe; nut shells (e.g., coconut shells, walnut shells, hazelnut shells, peanut shells, etc.); bamboo; rice husks; grass; corn stover; plant matter; seeds; paper; cardboard; manure; other agricultural residues; biorefining residues; sorghum; dried algae; coffee beans; coffee grounds; grounds; bagasse; and any combination thereof, as well as other possibilities.

[0015] The unactivated biomass-based carbon-containing particulate material is untreated other than being derived from a biomass feedstock that has undergone pyrolysis. In other words, the unactivated biomass-based carbon-containing particulate material has not been treated with steam or chemical treatment(s) that would activate the unactivated biomass-based carbon-containing particulate material and increase the porosity of the unactivated biomass-based carbon-containing particulate material, increase the specific surface area of ​​the unactivated biomass-based carbon-containing particulate material, and reduce the relative ash content of the unactivated biomass-based carbon-containing particulate material. The steam or chemical treatment(s) required to activate the unactivated biomass-based carbon-containing particulate material increases net carbon dioxide emissions, increases the carbon footprint, and increases the global warming potential of the thermoplastic foam composition. Using the unactivated biomass-based carbon-containing particulate material reduces carbon dioxide emissions by approximately 2.5 pounds per pound of unactivated biomass-based carbon-containing particulate material compared to activated biomass-based carbon-containing particulate material.

[0016] Unactivated biomass-based carbonaceous granular material is porous. The porosity of unactivated biomass-based carbonaceous granular material can be greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90% or greater than 95%. The porosity of unactivated biomass-based carbonaceous granular material can be between 50% and 90%, between 60% and 80%, between 65% and 75% or about 70%. It should be understood that the porosity of unactivated biomass-based carbonaceous granular material varies according to the specific biomass from which the unactivated biomass-based carbonaceous granular material is derived.

[0017] The specific surface area of ​​the unactivated biomass-based carbon-containing granular material may be between 150 square meters per gram of unactivated biomass-based carbon-containing granular material and 495 square meters per gram of unactivated biomass-based carbon-containing granular material. The specific surface area of ​​the unactivated biomass-based carbon-containing granular material may be between 190 square meters per gram of unactivated biomass-based carbon-containing granular material and 495 square meters per gram of unactivated biomass-based carbon-containing granular material, between 200 square meters per gram of unactivated biomass-based carbon-containing granular material and 485 square meters per gram of unactivated biomass-based carbon-containing granular material, between 250 square meters per gram of unactivated biomass-based carbon-containing granular material and 485 square meters per gram of unactivated biomass-based carbon-containing granular material, between 300 square meters per gram of unactivated biomass-based carbon-containing granular material and 485 square meters per gram of unactivated biomass-based carbon-containing granular material. The amount of carbon-containing granular material of the unactivated biomass-based carbon-containing granular material is between 200 m2 / g and 450 m2 / g of unactivated biomass-based carbon-containing granular material, between 200 m2 / g and 400 m2 / g of unactivated biomass-based carbon-containing granular material, between 200 m2 / g and 350 m2 / g of unactivated biomass-based carbon-containing granular material, or between 200 m2 / g and 300 m2 / g of unactivated biomass-based carbon-containing granular material.

[0018] The unactivated biomass-based carbon-containing particulate material may account for 0.1% to 25% by weight of the thermoplastic foam composition. In addition, the unactivated biomass-based carbon-containing particulate material may account for 0.5% to 20% by weight of the thermoplastic foam composition, 0.5% to 15% by weight of the thermoplastic foam composition, 0.5% to 12% by weight of the thermoplastic foam composition, 0.5% to 10% by weight of the thermoplastic foam composition, 0.5% to 8% by weight of the thermoplastic foam composition, 0.5% to 6% by weight of the thermoplastic foam composition, 0.5% to 5% by weight of the thermoplastic foam composition, 0.5% to 4% by weight of the thermoplastic foam composition, 0.5% to 3% by weight of the thermoplastic foam composition, 0.5% to 2% by weight of the thermoplastic foam composition, or 0.5% to 1% by weight of the thermoplastic foam composition. In addition, the unactivated biomass-based carbon-containing particulate material may comprise 1 wt % to 20 wt % of the thermoplastic foam composition, 1 wt % to 15 wt % of the thermoplastic foam composition, 1 wt % to 12 wt % of the thermoplastic foam composition, 1 wt % to 10 wt % of the thermoplastic foam composition, 1 wt % to 8 wt % of the thermoplastic foam composition, 1 wt % to 6 wt % of the thermoplastic foam composition, 1 wt % to 5 wt % of the thermoplastic foam composition, 1 wt % to 4 wt % of the thermoplastic foam composition, 1 wt % to 3 wt % of the thermoplastic foam composition, and 1 wt % to 2 wt % of the thermoplastic foam composition.

[0019] In addition, the unactivated biomass-based carbon-containing particulate material may comprise 2 wt % to 20 wt % of the thermoplastic foam composition, 2 wt % to 15 wt % of the thermoplastic foam composition, 2 wt % to 12 wt % of the thermoplastic foam composition, 2 wt % to 10 wt % of the thermoplastic foam composition, 2 wt % to 8 wt % of the thermoplastic foam composition, 2 wt % to 6 wt % of the thermoplastic foam composition, 2 wt % to 5 wt % of the thermoplastic foam composition, 2 wt % to 4 wt % of the thermoplastic foam composition, and 2 wt % to 3 wt % of the thermoplastic foam composition. In addition, the unactivated biomass-based carbon-containing particulate material may comprise 3 wt % to 20 wt % of the thermoplastic foam composition, 3 wt % to 15 wt % of the thermoplastic foam composition, 3 wt % to 12 wt % of the thermoplastic foam composition, 3 wt % to 10 wt % of the thermoplastic foam composition, 3 wt % to 8 wt % of the thermoplastic foam composition, 3 wt % to 6 wt % of the thermoplastic foam composition, 3 wt % to 5 wt % of the thermoplastic foam composition, and 3 wt % to 4 wt % of the thermoplastic foam composition.

[0020] It should be understood that the unactivated biomass-based carbonaceous particulate material may even account for more than 20% by weight of the thermoplastic foam composition. Although not required, the thermoplastic foam is generally petroleum-based. It should be understood that the unactivated biomass-based carbonaceous particulate material replaces the relative weight percentage of the thermoplastic foam in the thermoplastic foam composition. Thus, the higher weight percentage of the unactivated biomass-based carbonaceous particulate material in the thermoplastic foam composition reduces the relative weight percentage of the thermoplastic foam in the thermoplastic foam composition, thereby further reducing the carbon footprint of the thermoplastic foam composition.

[0021] A higher weight percentage of the unactivated biomass-based carbon-containing particulate material in the thermoplastic foam composition does not increase the melt pressure, and if processed by an extruder, does not increase the extruder torque. Thus, the encapsulation of the unactivated biomass-based carbon-containing particulate material in the thermoplastic foam composition does not increase the energy consumption during extrusion. The encapsulation of the unactivated biomass-based carbon-containing particulate material in the thermoplastic foam also has little significant effect on the viscosity or rheological behavior of the thermoplastic foam.

[0022] like Figure 1-Figure 3 As shown, the unactivated biomass-based carbonaceous particulate material can be evenly distributed and dispersed throughout the thermoplastic foam. It should be understood that Figure 1-Figure 3 is an image of a thermoplastic foam composition taken by a scanning electron microscope (SEM). The unactivated biomass-based carbon-containing particulate material is uniformly distributed throughout the thermoplastic foam so that any given section of the thermoplastic foam composition has approximately the same concentration of unactivated biomass-based carbon-containing particulate material. In addition, the unactivated biomass-based carbon-containing particulate material has a D50 particle size, and the D50 particle size may have a unimodal particle size distribution so that the unactivated biomass-based particulate material is uniformly dispersed throughout the thermoplastic foam. In other words, the unactivated biomass-based carbon-containing particulate material does not contain agglomerates that would produce a bimodal particle size distribution.

[0023] The D50 particle size of the unactivated biomass-based carbonaceous particulate material may be 0.1 micron to 200 microns. The D50 particle size represents the average diameter of the unactivated biomass-based carbonaceous particulate material measured according to ISO 13320. In addition, the D50 particle size of the unactivated biomass-based carbonaceous particulate material may be 0.2 microns to 200 microns, 0.2 microns to 100 microns, 0.2 microns to 50 microns, 0.2 microns to 40 microns, 0.2 microns to 30 microns, 0.2 microns to 20 microns, 0.2 microns to 15 microns, 0.2 microns to 12.5 microns, and 0.2 microns to 8 microns. In addition, the D50 particle size of the unactivated biomass-based carbonaceous particulate material can be 1 micron to 200 microns, 1 micron to 100 microns, 1 micron to 50 microns, 1 micron to 40 microns, 1 micron to 30 microns, 1 micron to 20 microns, 1 micron to 15 microns, 1 micron to 8 microns, about 1 micron, about 2 microns, about 3 microns, about 4 microns, about 5 microns, about 6 microns, about 7 microns, about 8 microns, about 9 microns, about 10 microns, about 11 microns, about 12 microns, about 13 microns, about 14 microns or about 15 microns. However, the average diameter of the unactivated biomass-based carbonaceous particulate material can even be less than 1 micron or greater than 100 microns.

[0024] The unactivated biomass-based carbonaceous particulate material may also have a non-uniform particle size ranging from 1 micron to 50 microns, from 1 micron to 35 microns, or from 2 microns to 25 microns. In addition, the D50 particle size of the unactivated biomass-based carbonaceous particulate material may be from 1 micron to 6 microns, from 1.5 microns to 6 microns, from 2 microns to 6 microns, from 2.5 microns to 6 microns, from 3 microns to 6 microns, from 3.5 microns to 6 microns, from 4 microns to 6 microns, from 4.5 microns to 6 microns, and from 5 microns to 6 microns. The smaller particle size of the unactivated biomass-based carbonaceous particulate material tends to increase the solubility of the thermoplastic foam composition.

[0025] The unactivated biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 75% measured according to ASTM D6866. It should be understood that the unactivated biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 75%. As a non-limiting example, the unactivated biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 80% measured according to ASTM D6866, the unactivated biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 85% measured according to ASTM D6866, the unactivated biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 90% measured according to ASTM D6866, the unactivated biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 95% measured according to ASTM D6866, and the unactivated biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) of about 100% measured according to ASTM D6866. In a non-limiting example, the unactivated biomass-based carbonaceous particulate material has a percent modern carbon (pMC) greater than 75%, an ash content less than 12%, and a nitrogen content less than 2%.

[0026] Thermoplastic foam can be further defined as an expanded thermoplastic foam formed by a blowing agent. Expanded thermoplastic foam can be formed by foaming with a blowing agent in an autoclave. However, it should also be understood that thermoplastic foam can be directly formed by extrusion with an extruder.

[0027] The thermoplastic foam composition may be self-extinguishing. In addition, although not required, the thermoplastic foam composition preferably does not contain a flame retardant other than the unactivated biomass-based carbonaceous particulate material. Although the unactivated biomass-based carbonaceous particulate material itself is combustible, it has been found that the thermoplastic foam composition comprising the thermoplastic foam and the unactivated biomass-based carbonaceous particulate material exhibits a flame retardant effect. As a non-limiting example, it was found that a molded article having a core density of 18 g / L and 5 wt% of the unactivated biomass-based carbonaceous particulate material is self-extinguishing. The thermoplastic foam composition may also be non-conductive.

[0028] Thermoplastic foams may define cells having a unimodal cell structure distribution, such as Figure 1-3 As shown. The unimodal cell structure distribution results in a uniform cell structure, which helps maintain the dimensional stability and mechanical properties of the thermoplastic foam composition. It is found that the encapsulation of the unactivated biomass-based carbonaceous particulate material in the thermoplastic foam both produces a unimodal cell structure distribution, resulting in a uniform cell structure, while also limiting the average size of the cells.

[0029] The cells may have an average size of less than 200 microns. The cells may also have an average size of less than 150 microns, less than 100 microns, less than 75 microns, or less than 50 microns. Limiting the average size of the cells further helps maintain the dimensional stability and mechanical properties of the thermoplastic foam composition. In addition, the cells may have an average size of 1 micron to 200 microns, 10 microns to 200 microns, 10 microns to 150 microns, 10 microns to 100 microns, 20 microns to 100 microns, 20 microns to 75 microns, and 20 microns to 50 microns.

[0030] In addition to the unactivated biomass-based carbonaceous granular material, the thermoplastic foam may be substantially free of cell nucleating agents. By comprising less than 1% by weight of cell nucleating agents, the thermoplastic foam may be substantially free of cell nucleating agents. The unactivated biomass-based carbonaceous granular material may serve as a nucleating agent for both isothermal crystallization and cell development. However, it is clear that the unactivated biomass-based carbonaceous granular material is not a too strong cell nucleating agent, such as other additives (e.g., talc), which interfere with the expansion of the cell and hinder the formation of a low-density thermoplastic foam composition. In addition, although the unactivated biomass-based carbonaceous granular material can promote cell nucleation, it may hinder cell growth during foaming. Therefore, since the unactivated biomass-based carbonaceous granular material is solid and does not actively promote foaming during foaming, a thermoplastic foam composition having both low density and high stiffness is an extraordinary achievement.

[0031] As described herein, the thermoplastic foam composition has a core density of 12 g / L to 400 g / L measured according to ASTM-D3575-W Test Method A. The core density of the thermoplastic foam composition can also be 12 g / L to 300 g / L, 12 g / L to 250 g / L, 12 g / L to 200 g / L, 12 g / L to 150 g / L, 12 g / L to 100 g / L, 12 g / L to 80 g / L, 12 g / L to 68 g / L, 12 g / L to 67.3 g / L, and 12 g / L to 45 g / L. The core densities listed herein are examples of low density products.

[0032] Also as described herein, the thermoplastic foam composition has an elastic modulus of 60 psi to 3500 psi measured according to ASTM-C203 Method I, Equation 13. The thermoplastic foam composition may also have an elastic modulus of 60 psi to 2500 psi, 60 psi to 2000 psi, 60 psi to 1000 psi, 200 psi to 2200 psi, 250 psi to 3500 psi, 500 psi to 3500 psi, 600 psi to 3500 psi, 100 The elastic modulus of the thermoplastic foam composition can be from 0 psi to 3500 psi, from 240 psi to 2100 psi, from 300 psi to 2100 psi, from 400 psi to 2000 psi, from 400 psi to 1500 psi, from 400 psi to 1000 psi, from 400 psi to 800 psi, or about 600 psi. It should be understood that the thermoplastic foam composition can have an elastic modulus of at least 600 psi, preferably at least 700 psi.

[0033] The elastic modulus of the thermoplastic foam composition may be at least 10% greater than the elastic modulus of a thermoplastic foam having the thermoplastic foam composition, but omitting the unactivated biomass-based carbonaceous particulate material, as measured according to ASTM-C203 Method I, Equation 13. As described herein, the encapsulation of the unactivated biomass-based carbonaceous particulate material increases the elastic modulus of the thermoplastic foam composition, thereby stiffening the thermoplastic foam composition. The elastic modulus of the thermoplastic foam composition may be at least 15% greater than the elastic modulus of a thermoplastic foam having the thermoplastic foam composition, but omitting the unactivated biomass-based carbonaceous particulate material, as measured according to ASTM-C203 Method I, Equation 13. The elastic modulus of the thermoplastic foam composition may even be at least 20% greater than the elastic modulus of a thermoplastic foam having the thermoplastic foam composition, but omitting the unactivated biomass-based carbonaceous particulate material, as measured according to ASTM-C203 Method I, Equation 13.

[0034] In addition, the unactivated biomass-based carbonaceous particulate material increases the elastic modulus of the thermoplastic foam composition compared to typical thermoplastic foams containing carbon black, while increasing or maintaining other desired mechanical properties of the thermoplastic foam composition. Typically, the addition of additives to typical thermoplastic foams has a significant negative impact on the mechanical properties of typical thermoplastic foams. However, it was unexpectedly discovered that encapsulation of the unactivated biomass-based carbonaceous particulate material maintains these other desired mechanical properties.

[0035] As a non-limiting example of the mechanical properties of the thermoplastic foam composition, the 25% strain compression set percentage of the thermoplastic foam composition can be within 25% of the 25% strain compression set percentage of a reference thermoplastic foam omitting the unactivated biomass-based carbon-containing particulate material as measured according to ASTM-D3575-B. The 25% strain compression set percentage of the thermoplastic foam composition can be within 20%, 15%, 10%, or even 5% of the 25% strain compression set percentage of a reference thermoplastic foam omitting the unactivated biomass-based carbon-containing particulate material as measured according to ASTM-D3575-B.

[0036] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the flexural strength of the thermoplastic foam composition can be within 10% of the flexural strength of a reference thermoplastic foam omitting the unactivated biomass-based carbon-containing particulate material as measured according to ASTM-C203. The flexural strength of the thermoplastic foam composition can be within 5% of the flexural strength of a reference thermoplastic foam omitting the unactivated biomass-based carbon-containing particulate material as measured according to ASTM-C203. The flexural strength of the thermoplastic foam composition may be between 5 psi and 125 psi, between 5 psi and 60 psi, between 6 psi and 110 psi, between 6 psi and 80 psi, between 6 psi and 50 psi, between 7 psi and 40 psi, between 8 psi and 50 psi, between 8 psi and 30 psi, between 9 psi and 25 psi, and between 10 psi and 20 psi.

[0037] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition may have a 50% strain compressive strength of at least 40 kPa measured according to ASTM-D3575-D. The thermoplastic foam composition may also have a 50% strain compressive strength of at least 60 kPa measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 80 kPa measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 100 kPa measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 150 kPa measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 200 kPa measured according to ASTM-D3575-D, or a 50% strain compressive strength of at least 250 kPa measured according to ASTM-D3575-D. The thermoplastic foam composition may even have a 50% strain compressive strength of at least 300 kPa measured according to ASTM-D3575-D. The thermoplastic foam composition has a 50% strain compressive strength of 40 kPa to 4100 kPa, 60 kPa to 3000 kPa, 100 kPa to 2000 kPa, 150 kPa to 1000 kPa, 200 kPa to 600 kPa, 250 kPa to 400 kPa, 300 kPa to 350 kPa, about 300 kPa, about 325 kPa, or about 350 kPa.

[0038] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition has a 75% strain compressive strength of 200 kPa to 13,500 kPa, 310 kPa to 10,000 kPa, 310 kPa to 5,000 kPa, 310 kPa to 3,000 kPa, 310 kPa to 2,000 kPa, 310 kPa to 1,000 kPa, 400 kPa to 800 kPa, 600 kPa to 800 kPa, 650 kPa to 750 kPa, or about 700 kPa.

[0039] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition has a tensile strength of between 200 kPa and 2800 kPa, between 200 kPa and 650 kPa, between 260 kPa and 2000 kPa, between 260 kPa and 1500 kPa, between 300 kPa and 1000 kPa, between 400 kPa and 800 kPa, between 500 kPa and 700 kPa, between 550 kPa and 650 kPa, or about 600 kPa.

[0040] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition has an elongation at break of 2% to 150%, 2% to 25%, 5% to 25%, 10% to 150%, 50% to 150%, 100% to 150%, 10% to 25%, 15% to 25%, 15% to 20%, about 15%, or about 20%.

[0041] Thermoplastic foam may include thermoplastic polyolefin (TPO), such as polyalkylene, including linear polymers, branched polymers or combinations thereof. Although not required, thermoplastic foam may include expanded polypropylene (EPP). Expanded polypropylene may be at least one selected from expanded polypropylene homopolymer, expanded polypropylene (random or block) copolymer and expanded polypropylene terpolymer. In other words, thermoplastic foam may be expanded polypropylene homopolymer, expanded polypropylene copolymer, expanded polypropylene terpolymer or combinations thereof. In a non-limiting example, thermoplastic foam may be high-density expanded polypropylene (HDPP), medium-density expanded polypropylene or low-density expanded polypropylene (LDPP). Although not required, compared with low-density polypropylene, a higher weight percentage of unactivated biomass-based carbonaceous particulate material may be used in high-density polypropylene.

[0042] In the embodiment where the thermoplastic foam is an expanded polypropylene copolymer or an expanded polypropylene terpolymer, the thermoplastic foam may include propylene monomer units and at least one selected from ethylene monomer units and butene monomer units or other α-olefin monomer units. As a non-limiting example, the expanded polypropylene terpolymer may be an expanded ethylene propylene 1-butene terpolymer.

[0043] In the embodiment where the expanded polypropylene includes propylene monomer units and at least one of ethylene monomer units and butene monomer units and other α-olefin monomer units, the propylene monomer units, ethylene monomer units, butene monomer units and / or other α-olefin monomer units may be arranged in a random configuration or an arranged configuration. More specifically, the propylene monomer units, ethylene monomer units, butene monomer units and / or other α-olefin monomer units may have a random or regular repeating pattern in the carbon skeleton of the expanded polymer. In addition, the stereoregularity of the propylene monomer units, ethylene monomer units, butene monomer units and / or other α-olefin monomer units may be arranged in an atactic configuration, wherein the repeating monomer units lack regularity or coordination when they are in their stereochemical orientation in the carbon skeleton of the expanded polymer; may be arranged in a syndiotactic configuration, wherein the repeating monomer units have regular alternation of different stereochemical orientations in the carbon skeleton of the expanded polymer; or may be arranged in an isotactic configuration, wherein all repeating monomer units have the same stereochemical orientation in the carbon skeleton of the expanded polymer. It should be understood that even expanded polypropylene homopolymers may be arranged in atactic, syndiotactic or isotactic configurations.

[0044] The expanded polypropylene may include at least 50 wt% of a random copolymer of polypropylene and 5 wt% to 30 wt% of ethylene propylene rubber. The expanded polypropylene may also include polyolefin elastomers and / or plastomers, such as Dow's Engage TM . The expanded polypropylene may be a recycled material or a new material. The expanded polypropylene may have a core density of 12 g / L to 68 g / L measured according to ASTM-D3575-W Test Method A. In addition, the expanded polypropylene may have a core density between 16 g / L and 68 g / L measured according to ASTM-D3575-W Test Method A, a core density between 12 g / L and 67.3 g / L measured according to ASTM-D3575-W Test Method A, a core density between 16 g / L and 50 g / L measured according to ASTM-D3575-W Test Method A, a core density between 16 g / L and 45 g / L measured according to ASTM-D3575-W Test Method A, or a core density between 20 g / L and 45 g / L measured according to ASTM-D3575-W Test Method A. The core densities listed herein are examples of low-density products.

[0045] In addition, the thermoplastic foam may include a thermoplastic elastomer obtained by polycondensation of a carboxylic acid polyamide and an alcohol-terminated polyether. The thermoplastic elastomer obtained by polycondensation of a carboxylic acid polyamide and an alcohol-terminated polyether may be Pebax sold by Arkema. The carboxylic acid polyamide may be, but is not limited to, nylon 6 (PA6), nylon 11 (PA11), and nylon 12 (PA12), and the alcohol-terminated polyether may be, but is not limited to, polytetramethylene glycol (PTMG) or polyethylene glycol (PEG).

[0046] As disclosed herein, the thermoplastic foam can be a polyolefin, such as expanded polypropylene. It is also contemplated that the thermoplastic foam can be other polyolefins, such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), medium density polyethylene (MDPE), polybutene-1 (PB-1), ethylene-octene copolymers, stereo block polypropylene, olefin block copolymers, propylene-butane copolymers, ethylene vinyl acetate copolymers (EVA), polyolefin elastomers (POE) or poly (alpha-olefins). However, the thermoplastic foam need not contain a polyolefin (e.g., expanded polypropylene). As non-limiting examples, it is also contemplated that the thermoplastic foam may include thermoplastic polyurethanes (TPU); polyamides (PA), such as nylon; polymethylpentene (PMP); polyisobutylene (PIB); styrene-butadiene block copolymers and hydrogenated products of the foregoing; polyesters, including but not limited to polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polycarbonate (PC); bioplastics, including but not limited to polylactic acid and polylactide (PLA), polybutylene adipate terephthalate (PBAT), poly(butylenesuccinate-co-butylene adipate), PBSA, polycaprolactone (PCL), polyhydroxyalkanoates (PHA), poly(3-hydroxybutyrate) (PHBH); poly(p-phenylene oxide) or poly(p-phenylene ether) (poly(p-phenylene oxide)). ether), PPE), including blends with polystyrene or high impact styrene-butadiene copolymers or polyamides; styrene polymers, including polystyrene, expandable polystyrene, styrene-acrylonitrile copolymers, styrene-methyl methacrylate copolymers, acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylate copolymers, including blends with polyphenylene ether (PPE) and / or polycarbonate (PC), styrene methyl methacrylate (SMMA), styrene-acrylonitrile (SAN), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS), styrene butadiene block copolymers (SBC), methyl methacrylate-butadiene-styrene (MBS) and styrene-ethylene-butylene-styrene (SEBS).

[0047] The thermoplastic foam composition may further include additives, such as additives configured to avoid thermal degradation of the thermoplastic foam composition during extrusion or during foaming in an autoclave, or such as additional colorants, stabilizers such as UV stabilizers, antistatic agents, flame retardants, metal deactivators, pigments, fillers, lubricants, and other carbon-based fillers, including but not limited to graphene, graphite, and expandable graphite. In addition, the thermoplastic foam composition may also include a resin for improving the foaming of the thermoplastic foam composition, and / or may include a coupling agent for better mixing and dispersion.

[0048] Thermoplastic polyurethane foam compositions for low-density and high-rigidity articles are also provided herein. Thermoplastic polyurethane foam compositions comprise thermoplastic polyurethane foam and biomass-based carbonaceous particulate material encapsulated in the thermoplastic polyurethane foam. Thermoplastic polyurethane foam compositions have a core density between 80 g / L and 400 g / L measured according to ASTM-D3575-W Test Method A. Thermoplastic polyurethane foam compositions have an elastic modulus between 60 psi and 700 psi measured according to ASTM-C203 Method I, Equation 13.

[0049] Biomass-based carbonaceous granular materials are non-petroleum-based additives, are renewable resources and sustainable, have low global warming potential (GWP), and leave a low carbon footprint. More specifically, biomass-based carbonaceous granular materials have a low carbon footprint because the biomass from which the biomass-based carbonaceous granular materials are derived sequesters carbon dioxide from the atmosphere during its life. In addition, biomass-based carbonaceous granular materials are suitable for encapsulation in thermoplastic foams to provide low-density products, while also adjusting the elastic modulus of the foam to provide high-rigidity products. Biomass-based carbonaceous granular materials can be a colorant that provides color to thermoplastic polyurethane foams, and are an ultraviolet (UV) stabilizer that prevents thermoplastic polyurethane foams from being degraded by exposure to ultraviolet energy.

[0050] Biomass-based carbonaceous particulate materials are derived from biomass feedstocks that have undergone pyrolysis, including, but not limited to, wood materials (e.g., wood, wood chips and / or leaves) from coniferous and / or deciduous trees, including maple trees, more specifically, rock maple trees, including their wood, wood chips and / or leaves, which are some of the most common maple leaves in Europe; nut shells (e.g., coconut shells, walnut shells, hazelnut shells, peanut shells, etc.); bamboo; rice husks; grass; corn stover; plant matter; seeds; paper; cardboard; manure; other agricultural residues; biorefining residues; sorghum; dried algae; coffee beans; coffee grounds; grounds; bagasse; and any combination thereof, as well as other possibilities.

[0051] The biomass-based carbonaceous granular material is porous. The porosity of the biomass-based carbonaceous granular material may be greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90% or greater than 95%. The porosity of the biomass-based carbonaceous granular material may be between 50% and 90%, between 60% and 80%, between 65% and 75% or about 70%. It should be understood that the porosity of the biomass-based carbonaceous granular material varies according to the specific biomass from which the biomass-based carbonaceous granular material is derived.

[0052] It is noteworthy that in the embodiments of the disclosed thermoplastic polyurethane foam composition, the biomass-based carbon-containing particulate material need not be unactivated. Instead, both activated biomass-based carbon-containing particulate material and unactivated biomass-based carbon-containing particulate material are considered suitable for encapsulation in thermoplastic polyurethane foam. The biomass-based carbon-containing particulate material may have a specific surface area between 150 square meters per gram of biomass-based carbon-containing particulate material and 2000 square meters per gram of biomass-based carbon-containing particulate material.

[0053] The biomass-based carbon-containing particulate material may be further defined as an unactivated biomass-based carbon-containing particulate material, and the unactivated biomass-based carbon-containing particulate material may have a specific surface area between 150 m2 / g of unactivated biomass-based carbon-containing particulate material and 495 m2 / g of unactivated biomass-based carbon-containing particulate material. The unactivated biomass-based carbon-containing granular material may have a specific surface area between 190 square meters per gram of unactivated biomass-based carbon-containing granular material and 495 square meters per gram of unactivated biomass-based carbon-containing granular material, may have a specific surface area between 200 square meters per gram of unactivated biomass-based carbon-containing granular material and 450 square meters per gram of unactivated biomass-based carbon-containing granular material, may have a specific surface area between 200 square meters per gram of unactivated biomass-based carbon-containing granular material and 400 square meters per gram of unactivated biomass-based carbon-containing granular material, may have a specific surface area between 200 square meters per gram of unactivated biomass-based carbon-containing granular material and 350 square meters per gram of unactivated biomass-based carbon-containing granular material, or may have a specific surface area between 200 square meters per gram of unactivated biomass-based carbon-containing granular material and 300 square meters per gram of unactivated biomass-based carbon-containing granular material.

[0054] Alternatively, the biomass-based carbonaceous granular material may be further defined as an activated biomass-based carbonaceous granular material, and the specific surface area of ​​the activated biomass-based carbonaceous granular material is between 495 m2 / g activated biomass-based carbonaceous granular material and 2000 m2 / g activated biomass-based carbonaceous granular material. The specific surface area of ​​the activated biomass-based carbonaceous granular material may be between 495 m2 / g activated biomass-based carbonaceous granular material and 1500 m2 / g activated biomass-based carbonaceous granular material, between 495 m2 / g activated biomass-based carbonaceous granular material and 1200 m2 / g activated biomass-based carbonaceous granular material, or between 495 m2 / g activated biomass-based carbonaceous granular material and 1000 m2 / g activated biomass-based carbonaceous granular material. For example, the activated biomass-based carbonaceous granular material is treated with steam and / or chemical treatment (one or more).

[0055] Furthermore, the thermoplastic polyurethane foam composition may be recyclable.Although the thermoplastic polyurethane foam composition may include cross-links, these cross-links do not reach the extent that the thermoplastic polyurethane foam is a thermoset material.

[0056] The biomass-based carbon-containing particulate material may account for 0.1% to 25% by weight of the thermoplastic polyurethane foam composition. In addition, the biomass-based carbon-containing particulate material may account for 0.5% to 20% by weight of the thermoplastic polyurethane foam composition, 0.5% to 15% by weight of the thermoplastic polyurethane foam composition, 0.5% to 12% by weight of the thermoplastic polyurethane foam composition, 0.5% to 10% by weight of the thermoplastic polyurethane foam composition, 0.5% to 8% by weight of the thermoplastic polyurethane foam composition, 0.5% to 6% by weight of the thermoplastic polyurethane foam composition, 0.5% to 5% by weight of the thermoplastic polyurethane foam composition, 0.5% to 4% by weight of the thermoplastic polyurethane foam composition, 0.5% to 3% by weight of the thermoplastic polyurethane foam composition, 0.5% to 2% by weight of the thermoplastic polyurethane foam composition, and 0.5% to 1% by weight of the thermoplastic polyurethane foam composition. Additionally, the biomass-based carbon-containing particulate material may comprise 1 wt % to 20 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 15 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 12 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 10 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 8 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 6 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 5 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 4 wt % of the thermoplastic polyurethane foam composition, 1 wt % to 3 wt % of the thermoplastic polyurethane foam composition, and 1 wt % to 2 wt % of the thermoplastic polyurethane foam composition.

[0057] In addition, the biomass-based carbon-containing particulate material can comprise 2 wt % to 20 wt % of the thermoplastic polyurethane foam composition, 2 wt % to 15 wt % of the thermoplastic polyurethane foam composition, 2 wt % to 12 wt % of the thermoplastic polyurethane foam composition, 2 wt % to 10 wt % of the thermoplastic polyurethane foam composition, 2 wt % to 8 wt % of the thermoplastic polyurethane foam composition, 2 wt % to 6 wt % of the thermoplastic polyurethane foam composition, 2 wt % to 5 wt % of the thermoplastic polyurethane foam composition, 2 wt % to 4 wt % of the thermoplastic polyurethane foam composition, and 2 wt % to 3 wt % of the thermoplastic polyurethane foam composition. In addition, the biomass-based carbon-containing particulate material can comprise 3 wt % to 20 wt % of the thermoplastic polyurethane foam composition, 3 wt % to 15 wt % of the thermoplastic polyurethane foam composition, 3 wt % to 12 wt % of the thermoplastic polyurethane foam composition, 3 wt % to 10 wt % of the thermoplastic polyurethane foam composition, 3 wt % to 8 wt % of the thermoplastic polyurethane foam composition, 3 wt % to 6 wt % of the thermoplastic polyurethane foam composition, 3 wt % to 5 wt % of the thermoplastic polyurethane foam composition, and 3 wt % to 4 wt % of the thermoplastic polyurethane foam composition.

[0058] It should be understood that the biomass-based carbon-containing particulate material may even account for more than 20% by weight of the thermoplastic polyurethane foam composition. Although not required, the thermoplastic polyurethane foam is generally petroleum-based. It should be understood that the biomass-based carbon-containing particulate material can replace the relative weight percentage of the thermoplastic polyurethane foam in the thermoplastic polyurethane foam composition. Thus, the higher weight percentage of the biomass-based carbon-containing particulate material in the thermoplastic polyurethane foam composition reduces the relative weight percentage of the thermoplastic polyurethane foam in the thermoplastic polyurethane foam composition, thereby further reducing the carbon footprint of the thermoplastic polyurethane foam composition.

[0059] A higher weight percentage of biomass-based carbon-containing particulate material in the thermoplastic polyurethane foam composition does not increase the melt pressure, and if processed by an extruder, does not increase the extruder torque. Thus, the encapsulation of the biomass-based carbon-containing particulate material in the thermoplastic polyurethane foam composition does not increase the energy consumption during extrusion. The encapsulation of the biomass-based carbon-containing particulate material in the thermoplastic polyurethane foam also has little significant effect on the viscosity or rheological behavior of the thermoplastic polyurethane foam.

[0060] The biomass-based carbon-containing particulate material can be evenly distributed and evenly dispersed throughout the thermoplastic polyurethane foam. The biomass-based carbon-containing particulate material is evenly distributed throughout the thermoplastic polyurethane foam so that any given section of the thermoplastic polyurethane foam composition has approximately the same concentration of biomass-based carbon-containing particulate material. In addition, the biomass-based carbon-containing particulate material has a D50 particle size, and the D50 particle size can have a unimodal particle size distribution so that the biomass-based particulate material is evenly dispersed throughout the thermoplastic polyurethane foam. In other words, the biomass-based carbon-containing particulate material does not contain agglomerates that would produce a bimodal particle size distribution.

[0061] The D50 particle size of the biomass-based carbonaceous particulate material may be 0.1 micron to 200 microns. The D50 particle size represents the average diameter of the biomass-based carbonaceous particulate material measured according to ISO 13320. In addition, the D50 particle size of the biomass-based carbonaceous particulate material may be 0.2 micron to 200 microns, 0.2 micron to 100 microns, 0.2 micron to 50 microns, 0.2 micron to 40 microns, 0.2 micron to 30 microns, 0.2 micron to 20 microns, 0.2 micron to 15 microns, 0.2 micron to 12.5 microns, and 0.2 micron to 8 microns. In addition, the D50 particle size of the biomass-based carbonaceous particulate material can be 1 micron to 200 microns, 1 micron to 100 microns, 1 micron to 50 microns, 1 micron to 40 microns, 1 micron to 30 microns, 1 micron to 20 microns, 1 micron to 15 microns, 1 micron to 8 microns, about 1 micron, about 2 microns, about 3 microns, about 4 microns, about 5 microns, about 6 microns, about 7 microns, about 8 microns, about 9 microns, about 10 microns, about 11 microns, about 12 microns, about 13 microns, about 14 microns, or about 15 microns. However, the average diameter of the biomass-based carbonaceous particulate material can even be less than 1 micron or greater than 100 microns.

[0062] The biomass-based carbonaceous particulate material may also have a non-uniform particle size ranging from 1 micron to 50 microns, 1 micron to 35 microns, or 2 microns to 25 microns. In addition, the D50 particle size of the biomass-based carbonaceous particulate material may be 1 micron to 6 microns, 1.5 microns to 6 microns, 2 microns to 6 microns, 2.5 microns to 6 microns, 3 microns to 6 microns, 3.5 microns to 6 microns, 4 microns to 6 microns, 4.5 microns to 6 microns, and 5 microns to 6 microns. The smaller particle size of the biomass-based carbonaceous particulate material tends to increase the solubility of the thermoplastic foam composition.

[0063] The biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 75% measured according to ASTM D6866. It should be understood that the biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 75%. As a non-limiting example, the biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 80% measured according to ASTM D6866, the biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 85% measured according to ASTM D6866, the biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 90% measured according to ASTM D6866, the biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) greater than 95% measured according to ASTM D6866, and the biomass-based carbon-containing particulate material may have a modern carbon percentage (pMC) of about 100% measured according to ASTM D6866. In a non-limiting example, the biomass-based carbonaceous particulate material has a percent modern carbon (pMC) greater than 75%, an ash content less than 12%, and a nitrogen content less than 2%.

[0064] Thermoplastic polyurethane foam can be further defined as expanded thermoplastic polyurethane foam formed by a blowing agent. Expanded thermoplastic polyurethane foam can be formed by foaming with a blowing agent in an autoclave. However, it should also be understood that thermoplastic polyurethane foam can be directly formed by extrusion with an extruder.

[0065] The thermoplastic polyurethane foam composition may be self-extinguishing. In addition, although not required, the thermoplastic polyurethane foam composition preferably does not contain a flame retardant other than the biomass-based carbonaceous particulate material. Although the biomass-based carbonaceous particulate material itself is combustible, it has been found that the thermoplastic polyurethane foam composition comprising the thermoplastic polyurethane foam and the biomass-based carbonaceous particulate material exhibits a flame retardant effect. The thermoplastic polyurethane foam composition may also be non-conductive.

[0066] The thermoplastic polyurethane foam can define cells having a unimodal cell structure distribution. The unimodal cell structure distribution results in a uniform cell structure, which helps maintain the dimensional stability and mechanical properties of the thermoplastic polyurethane foam composition. It was found that encapsulation of biomass-based carbon-containing particulate material in thermoplastic polyurethane foam both produces a unimodal cell structure distribution, resulting in a uniform cell structure, while also limiting the average size of the cells.

[0067] The foam cells may have an average size of less than 200 microns. The foam cells may also have an average size of less than 150 microns, less than 100 microns, less than 75 microns, or less than 50 microns. Limiting the average size of the foam cells further helps maintain the dimensional stability and mechanical properties of the thermoplastic polyurethane foam composition. In addition, the foam cells may have an average size of 1 micron to 200 microns, 10 microns to 200 microns, 10 microns to 150 microns, 10 microns to 100 microns, 20 microns to 100 microns, 20 microns to 75 microns, and 20 microns to 50 microns.

[0068] In addition to the biomass-based carbonaceous granular material, the thermoplastic polyurethane foam may not contain a cell nucleating agent. By comprising a cell nucleating agent less than 1% by weight, the thermoplastic polyurethane foam may be substantially free of a cell nucleating agent. The biomass-based carbonaceous granular material may serve as a nucleating agent for both isothermal crystallization and cell development. However, it is clear that the biomass-based carbonaceous granular material is not a too strong cell nucleating agent, such as other additives (e.g., talcum), which interfere with the expansion of the cell and hinder the formation of a low-density thermoplastic polyurethane foam composition. In addition, although the biomass-based carbonaceous granular material can promote cell nucleation, it may hinder cell growth during foaming. Therefore, since the biomass-based carbonaceous granular material is solid and does not actively promote expansion during foaming, the thermoplastic polyurethane foam composition having both low density and high rigidity is an extraordinary achievement.

[0069] As described herein, the thermoplastic polyurethane foam composition has a core density of 80 g / L to 400 g / L measured according to ASTM-D3575-W Test Method A. The core density of the thermoplastic polyurethane foam composition can also be 100 g / L to 300 g / L, 150 g / L to 250 g / L, 100 g / L to 200 g / L, and 100 g / L to 150 g / L. The core densities listed herein are exemplary of low density products.

[0070] Also as described herein, the thermoplastic polyurethane foam composition has an elastic modulus of 60 to 700 psi measured according to ASTM-C203 Method I, Equation 13. The thermoplastic polyurethane foam composition may also have an elastic modulus of 60 to 500 psi, 80 to 400 psi, 100 to 350 psi, or 150 to 300 psi. It should be understood that the thermoplastic polyurethane foam composition may have an elastic modulus of at least 100 psi.

[0071] The elastic modulus of the thermoplastic polyurethane foam composition may be at least 10% greater than the elastic modulus of a thermoplastic polyurethane foam having a thermoplastic polyurethane foam composition, but omitting the biomass-based carbon-containing particulate material, as measured according to ASTM-C203 Method I, Equation 13. As described herein, the encapsulation of the biomass-based carbon-containing particulate material increases the elastic modulus of the thermoplastic polyurethane foam composition, thereby stiffening the thermoplastic polyurethane foam composition. The elastic modulus of the thermoplastic polyurethane foam composition may be at least 15% greater than the elastic modulus of a thermoplastic polyurethane foam having a thermoplastic polyurethane foam composition, but omitting the biomass-based carbon-containing particulate material, as measured according to ASTM-C203 Method I, Equation 13. The elastic modulus of the thermoplastic polyurethane foam composition may even be at least 20% greater than the elastic modulus of a thermoplastic polyurethane foam having a thermoplastic polyurethane foam composition, but omitting the biomass-based carbon-containing particulate material, as measured according to ASTM-C203 Method I, Equation 13.

[0072] In addition, the biomass-based carbon-containing particulate material increases the elastic modulus of the thermoplastic polyurethane foam composition compared to typical thermoplastic polyurethane foams containing carbon black, while maintaining other desired mechanical properties of the thermoplastic polyurethane foam composition. Typically, the addition of additives to typical thermoplastic polyurethane foams has a significant negative impact on the mechanical properties of typical thermoplastic polyurethane foams. However, it was unexpectedly discovered that encapsulation of the biomass-based carbon-containing particulate material maintains these other desired mechanical properties.

[0073] As a non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the 25% strain compression set percentage of the thermoplastic polyurethane foam composition can be within 25% of the 25% strain compression set percentage of a reference thermoplastic polyurethane foam that omits the biomass-based carbon-containing particulate material as measured according to ASTM-D3575-B. The 25% strain compression set percentage of the thermoplastic polyurethane foam composition can be within 20%, 15%, 10%, or even 5% of the 25% strain compression set percentage of a reference thermoplastic polyurethane foam that omits the biomass-based carbon-containing particulate material as measured according to ASTM-D3575-B.

[0074] As another non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the flexural strength of the thermoplastic polyurethane foam composition may be within 10% of the flexural strength of a reference thermoplastic polyurethane foam omitting the biomass-based carbonaceous particulate material as measured according to ASTM-C203. The flexural strength of the thermoplastic polyurethane foam composition may be within 5% of the flexural strength of a reference thermoplastic polyurethane foam omitting the biomass-based carbonaceous particulate material as measured according to ASTM-C203. The flexural strength of the thermoplastic polyurethane foam composition may be between 5 psi and 80 psi, between 5 psi and 60 psi, between 6 psi and 50 psi, between 7 psi and 40 psi, between 8 psi and 30 psi, between 9 psi and 25 psi, and between 10 psi and 20 psi.

[0075] As another non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the thermoplastic polyurethane foam composition may have a 50% strain compressive strength of at least 40 kilopascals measured according to ASTM-D3575-D. The thermoplastic polyurethane foam composition may also have a 50% strain compressive strength of at least 60 kilopascals measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 80 kilopascals measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 100 kilopascals measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 150 kilopascals measured according to ASTM-D3575-D, a 50% strain compressive strength of at least 200 kilopascals measured according to ASTM-D3575-D, or a 50% strain compressive strength of at least 250 kilopascals measured according to ASTM-D3575-D. The thermoplastic polyurethane foam composition may even have a 50% strain compressive strength of at least 300 kPa measured according to ASTM-D3575-D. The thermoplastic polyurethane foam composition has a 50% strain compressive strength of 40 kPa to 1500 kPa, 40 kPa to 1000 kPa, 40 kPa to 800 kPa, 40 kPa to 600 kPa, 40 kPa to 500 kPa, 60 kPa to 1500 kPa, 100 kPa to 1500 kPa, 150 kPa to 1000 kPa, 200 kPa to 600 kPa, 250 kPa to 400 kPa, 300 kPa to 350 kPa, about 300 kPa, about 325 kPa, or about 350 kPa.

[0076] As another non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the thermoplastic polyurethane foam composition has a mechanical property of 80 kPa to 13500 kPa, 80 kPa to 3000 kPa, 150 kPa to 3000 kPa, 200 kPa to 3000 kPa, 300 kPa to 3000 kPa, 400 kPa to 3000 kPa, 500 kPa to 3000 kPa, 310 kPa to 3000 kPa, 310 kPa to 3000 kPa, 30 ... 75% strain compressive strength of 1000 kPa to 10000 kPa, 310 kPa to 5000 kPa, 310 kPa to 3000 kPa, 310 kPa to 2000 kPa, 310 kPa to 1000 kPa, 400 kPa to 800 kPa, 600 kPa to 800 kPa, 650 kPa to 750 kPa, about 700 kPa, about 800 kPa, about 900 kPa or about 1000 kPa.

[0077] The thermoplastic polyurethane foam composition may further include additives, such as additives configured to avoid thermal degradation of the thermoplastic polyurethane foam composition during extrusion or during foaming in an autoclave, or such as additional colorants, stabilizers such as UV stabilizers, antistatic agents, flame retardants, metal deactivators, pigments, fillers, lubricants and other carbon-based fillers, including but not limited to graphene, graphite and expandable graphite. In addition, the thermoplastic polyurethane foam composition may also include a resin for improving the foaming of the thermoplastic polyurethane foam composition, and / or may include a coupling agent for better mixing and dispersion.

[0078] Thermoplastic foam compositions, including thermoplastic polyurethane foam compositions, can be formed into beads or final products (e.g., low density and high stiffness products). It should be understood that the final product can be a component of a larger assembly. The final product can be used in automotive applications. In a non-limiting example of automotive applications, the final product can be a seat substrate, a seat cushion, a headrest, a bumper core, an armrest, a trunk or cargo space component, a door panel component, a headliner component, a spacer, a load floor, or a battery case. It should also be understood that the final product does not need to be an automotive application. In a non-limiting example of non-automotive applications, the final product can be a shoe component, such as a shoe midsole or a shoe insole, a packaging tray, a protective packaging box, an industrial dunnage, and an industrial packaging. In embodiments where the thermoplastic foam composition comprises expanded polypropylene, the article may be, inter alia, a seat substrate, or a trunk or cargo space component.The thermoplastic polyurethane foam composition may be particularly suitable for articles such as bumpers and shoe components, such as midsoles or insoles.

[0079] It should be understood that the unactivated biomass-based carbonaceous granular material affects the foamability, solubility and performance of the beads. If the final product is subsequently formed, the unactivated biomass-based carbonaceous granular material will also affect the processability, cell morphology, thermal characteristics and final performance of the beads. The thermoplastic foam composition may also include two separate crystalline melting points. In other words, the thermoplastic foam composition may have a low crystalline melting point and a high crystalline melting point. As discussed below, the low crystalline melting point and the high crystalline melting point improve the processability of the thermoplastic foam composition. In addition, it is also found that the unactivated biomass-based carbonaceous granular material can reduce the low crystalline melting point of the thermoplastic foam composition, the high crystalline melting point of the thermoplastic foam composition, or reduce the low crystalline melting point and the high crystalline melting point of the thermoplastic foam composition. As a non-limiting example, the low crystalline melting point may be between 110 degrees Celsius and 150 degrees Celsius, and the high crystalline melting point may be between 150 degrees Celsius and 170 degrees Celsius.

[0080] Also provided is a method of making a thermoplastic foam composition. The method may include the steps of extruding a thermoplastic material and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic material. The thermoplastic material may be directly extruded as a thermoplastic foam. Alternatively, the method may include the steps of expanding the thermoplastic material to form a thermoplastic foam and the unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam.

[0081] The step of extruding the thermoplastic material can be completed with an extruder, and the extruder includes but is not limited to a single screw extruder or a twin screw extruder. Although not required, the length to diameter ratio of the extruder is about 36:1, and the extruder may have a rough (harsh) screw geometry. The step of extruding the thermoplastic material melt blends the thermoplastic material with the unactivated biomass-based carbonaceous granular material. The step of extruding the thermoplastic material may further include, optionally in a variety of different resins, and optionally together with one or more additives, extruding the unactivated biomass-based carbonaceous granular material of various different particle sizes. The relative weight percentage of the unactivated biomass-based carbonaceous granular material in the thermoplastic foam composition will not significantly affect the rheological properties (such as viscosity) of the thermoplastic foam composition, therefore will not significantly affect the melt pressure and extruder torque, and therefore will not increase the energy consumption of the extruder during the step of extruding the thermoplastic material. Thus, the unactivated biomass-based carbonaceous granular material will not negatively affect carbon dioxide emissions or the carbon footprint of the method. The step of extruding the thermoplastic material may include cooling the extruded thermoplastic material in a water bath and granulating the extruded thermoplastic material into pellets using a pelletizer. Granulating the extruded thermoplastic material into pellets using a pelletizer may be completed before the pellets contact the water bath. It should also be understood that the extrusion step may form a film as thin as 40 microns.

[0082] The step of expanding thermoplastic material to form thermoplastic foam and the unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam can be completed with autoclave and can further include the use of a foaming agent. The temperature of the autoclave can be set to between about 80 degrees Celsius and about 250 degrees Celsius, between about 80 degrees Celsius and about 200 degrees Celsius, between about 100 degrees Celsius and about 180 degrees Celsius, between about 120 degrees Celsius and about 150 degrees Celsius, between about 125 degrees Celsius and about 140 degrees Celsius, between about 125 degrees Celsius and about 135 degrees Celsius, about 125 degrees Celsius, about 130 degrees Celsius or about 135 degrees Celsius. Thermoplastic material can be disposed in autoclave for 1 minute to 2 hours, 20 minutes to 1 hour or about 1 hour. The step of expanding the thermoplastic material to form a thermoplastic foam composition can also be completed under pressure. More specifically, the thermoplastic material may be under pressure, such as, but not limited to, between 200 psi and 1200 psi, between 500 psi and 1100 psi, between 600 psi and 1000 psi, between 700 psi and 900 psi, or about 800 psi. The specific temperature and pressure associated with the step of expanding the thermoplastic material may be determined according to the specific thermoplastic material to avoid the risk of cracking the thermoplastic material.

[0083] The step of expanding the thermoplastic material to form a thermoplastic foam composition may further include mixing the thermoplastic material with a suspension stabilizer and optionally water, and may further include impregnating the thermoplastic material with a gas or liquid, such as but not limited to carbon dioxide, nitrogen or a combination thereof. The step of expanding the thermoplastic material may further include decompressing the thermoplastic material so that the thermoplastic material expands to form a thermoplastic foam composition due to the thermodynamic instability caused by the sharp pressure drop. Although not required, the step of expanding the thermoplastic material may be completed by two or more separate expansions, each subsequent expansion further reducing the density of the thermoplastic foam composition. The step of expanding the thermoplastic material may further include washing the thermoplastic foam composition with water, optionally deionized water, to remove the suspension stabilizer (if present).

[0084] Unactivated biomass-based carbonaceous granular materials can serve as cell nucleation sites, such as heterogeneous cell nucleation sites, or as crystallization nucleating agents during the step of expanding the thermoplastic material to form a thermoplastic foam composition. Thus, no additional additive is required to serve as a nucleation site or nucleating agent. In addition, unactivated biomass-based carbonaceous granular materials can be used to limit the size of the pores defined by the thermoplastic foam composition, thereby also increasing the uniformity of the pores. It should be understood that unactivated biomass-based carbonaceous granular materials are solids, and may not play a role in increasing the size of the pores during the step of expanding the thermoplastic material to form a thermoplastic foam composition. Therefore, it should be understood that a thermoplastic foam composition comprising a thermoplastic foam and an unactivated biomass-based carbonaceous granular material encapsulated in the thermoplastic foam is an important improvement, and the thermoplastic foam composition also has a high elongation at break, a controlled crystallization rate, and good rheological properties. As described above, the thermoplastic foam composition may include other additives in addition to the unactivated biomass-based carbonaceous granular material. In another non-limiting example, the thermoplastic foam composition may include additional nucleation sites and / or additional cell nucleating agents, which may be referred to as co-nucleating agents, for crystallization during the step of expanding the thermoplastic material to form the thermoplastic foam composition.

[0085] The step of expanding the thermoplastic material may be further defined as a step of expanding the pellets to form expanded beads. Thus, the step of expanding the pellets may further include mixing the pellets with a suspension stabilizer and optionally water, and may further include impregnating the pellets with a gas (such as, but not limited to, carbon dioxide) by pressurizing the pellets as described herein. The step of expanding the pellets may further include decompressing the pellets so that the pellets expand to form expanded beads comprising a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam. Due to the thermodynamic instability generated by the sharp pressure drop, the pellets expand to form expanded beads. The step of expanding the pellets may further include washing the expanded beads with water, optionally deionized water, to remove the suspension stabilizer (if present).

[0086] The method may further include the step of forming a final product with a thermoplastic foam composition, the thermoplastic foam composition comprising a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated by the thermoplastic foam. The step of forming the final product can be completed with a press (such as but not limited to a steam chamber press, a hydraulic press or a resin press) to form the final product. Additionally or alternatively, the step of forming the final product can be completed by bonding using an adhesive (such as glue). Pressure can cause the thermoplastic foam composition to sinter. More specifically, in an embodiment in which expanded beads are formed, the expanded beads can be sintered. It should be understood that the carbon footprint of the method can be further reduced by using a press with low steam pressurization. It should also be understood that, depending on the specific formulation of the thermoplastic foam composition and the specific processing parameters, the low crystalline melting point of the thermoplastic foam composition can be reduced compared to a similar composition containing carbon black instead of unactivated biomass-based carbonaceous particulate material, thereby further reducing the carbon footprint of the method.

[0087] As described herein, the thermoplastic foam composition may include a low crystalline melting point and a high crystalline melting point, which may be collectively referred to as a dual melt curve. More specifically, the expanded beads may include a low crystalline melting point and a high crystalline melting point. The step of forming the final product with the thermoplastic foam composition greatly benefits from the low crystalline melting point and the high crystalline melting point. More specifically, when the temperature of the press (e.g., steam temperature) is selected during the step of forming the final product, the temperature of the press is advantageously between the low crystalline melting point and the high crystalline melting point, or the temperature of the press is advantageously below the high crystalline melting point to ensure the structural integrity of the final product. Thus, during the step of forming the final product, the crystals with a low crystalline melting point will melt, thereby facilitating the sintering of the thermoplastic foam composition, but the crystals with a high crystalline melting point will not melt, thereby facilitating the maintenance of the overall shape of the final product. As a non-limiting example, a thermoplastic foam composition comprising an expanded ethylene propylene 1-butene terpolymer and 10 wt % of an unactivated biomass-based carbonaceous particulate material encapsulated in the expanded ethylene propylene 1-butene terpolymer has a low crystalline melting point and a high crystalline melting point (i.e., a dual melt curve), and thus the final product formed from the thermoplastic foam composition does not have any sintering problem or dimensional stability problem.

[0088] Although not intending to be bound by theory, it is contemplated that encapsulating the unactivated biomass-based carbon-containing particulate material in the thermoplastic foam of the thermoplastic foam composition will increase the dimensional stability of the thermoplastic foam composition. Typically, after forming the final product, the final product must be placed in a high temperature chamber or container (e.g., a "hot chamber") to reduce the possibility of changes in the dimensions of the article, such as being placed at a temperature of about 80 degrees Celsius or less for about 4 to 8 hours. During this period of time at high temperature, the typical final product is stable and the pressure within the individual cells is balanced, so that the dimensions of the typical final product do not change much (if any) compared to just after formation. If the typical final product is not placed in a high temperature chamber or container for a period of time, the dimensions of the final product will change, most likely to the extent that the final product will be out of tolerance.

[0089] However, it was found that the encapsulation of the unactivated biomass-based carbonaceous particulate material in the thermoplastic foam improves the dimensional stability of the thermoplastic foam composition, so that the final product formed from the thermoplastic foam composition does not need to be placed in a high temperature chamber or container. Although not intending to be bound by theory, it is believed that the unactivated biomass-based carbonaceous particulate material makes the heat distribution during and after the formation of the final product (e.g., during and after molding) more uniform. This uniformity of heat distribution also makes the relative pressure in each cell of the thermoplastic foam composition more uniform, thereby maintaining the size of the final product. Maintaining the size of the final product is important to ensure that the final product is within the correct tolerance range for the final product.

[0090] Also provided is a method for making a thermoplastic polyurethane foam composition. The method may include the steps of extruding a thermoplastic polyurethane material and a biomass-based carbonaceous particulate material encapsulated in the thermoplastic polyurethane material. The thermoplastic polyurethane material may be directly extruded as a thermoplastic polyurethane foam. Alternatively, the method may include the steps of expanding the thermoplastic polyurethane material to form a thermoplastic polyurethane foam and a biomass-based carbonaceous particulate material encapsulated in the thermoplastic polyurethane foam.

[0091] The following examples are intended to illustrate the present disclosure and are not to be construed as limiting the scope of the present disclosure in any way.

[0092] Examples 1-5

[0093] Examples 1-5 are thermoplastic foam compositions according to the subject disclosure and can be found in Tables 1-3. Each of Examples 1-5 corresponds to Tests 1-5 in Tables 1-3, respectively. The thermoplastic foam compositions used in Tests 1-5 of Tables 1-3 have the same composition, i.e., thermoplastic foam compositions comprising expanded polypropylene and 5% by weight of unactivated biomass-based carbonaceous particulate material, but they are produced under different processing parameters. Controls 1 and 2 of Tables 1-3 are not formed according to the subject disclosure, but are included to highlight the advantages of the thermoplastic foam compositions described herein. More specifically, Controls 1 and 2 include typical foam compositions comprising expanded polypropylene and 3% by weight of carbon black.

[0094] Referring now to Table 1, the thermoplastic foam compositions of Tests 1-5 were formed to have core densities ranging between 17.9 g / L and 56.4 g / L as measured according to ASTM-D3575-W Test Method A. As can be seen from Table 1, each of Tests 1-5 had an elastic modulus ranging from 406.4 psi to 2009.3 psi as measured according to ASTM-C203 Method I, Equation 13. Comparing Tests 1-5 in Table 1 with Controls 1 and 2, it is apparent that encapsulation of the unactivated biomass-based carbonaceous particulate material increases the elastic modulus of the thermoplastic foam composition. More specifically, now comparing Test 4 and Control 1, despite having similar nominal densities and similar core densities, Test 4 has a much higher elastic modulus. The elastic modulus of Test 4 is 801.8, while the elastic modulus of Control 1 is only 670.1. Therefore, it is apparent that the elastic modulus of Test 4 is nearly 20% greater than the elastic modulus of the reference thermoplastic foam (eg, Control 1) that omits the unactivated biomass-based carbon-containing particulate material.

[0095] Still referring to Table 1, each of Tests 1-5 also measured the 25% strain and 50% strain compression permanent deformation percentage according to ASTM-3575-B. The 25% strain compression permanent deformation percentage of Tests 1-5 ranged from 4-16%, while the 50% strain compression permanent deformation percentage of Tests 1-5 ranged from 22-27%. Comparing Tests 1-5 in Table 1 with Controls 1 and 2, it is clear that the 25% strain and 50% strain compression permanent deformation percentages are not reduced much (if any) in the case of encapsulating the unactivated biomass-based carbonaceous particulate material. More specifically, now comparing Test 4 with Control 1, it can be seen that the similar nominal density, similar core density, similar 25% strain compression permanent deformation percentage and similar 50% strain compression permanent deformation percentage of the two. Therefore, it is clear that the 25% strain compression permanent deformation percentage of Test 4 is within 25% of the 25% strain compression permanent deformation percentage of the reference thermoplastic foam (e.g., Control 1) that omits the unactivated biomass-based carbonaceous particulate material. It is also apparent that the 50% strain compression set percentage of Test 4 is within 25% of the 50% strain compression set percentage of the reference thermoplastic foam (eg, Control 1) that omits the unactivated biomass-based carbonaceous particulate material.

[0096] Referring now to Table 2, each of Tests 1-5 further measured the flexural strength according to ASTM-C203. The flexural strength of Tests 1-5 ranged from 10.4 pounds per square inch to 53.1 pounds per square inch. Comparing Tests 1-5 in Table 2 with Controls 1 and 2, it is apparent that the flexural strength is not reduced much (if at all) in the case of encapsulating the unactivated biomass-based carbonaceous particulate material. More specifically, now comparing Test 4 with Control 1, it can be seen that the two have similar nominal densities, similar core densities, and similar flexural strengths. Therefore, it is apparent that the flexural strength of Test 4 is within 10% of the flexural strength of the reference thermoplastic foam (e.g., Control 1) in which the unactivated biomass-based carbonaceous particulate material is omitted. Similar conclusions can be drawn after comparing the 10% strain, 25% strain, 50% strain, and 75% strain compressive strengths.

[0097] Referring now to Table 3, each of Tests 1-5 further measured the tensile strength and tensile elongation according to ASTM-3575-T. After reviewing Table 3, a similar conclusion can be drawn that the encapsulation effect of the unactivated biomass-based carbon-containing particulate material is related to the tensile strength and tensile elongation. Thus, it is clear that the encapsulation of the unactivated biomass-based carbon-containing particulate material does not negatively affect the physical properties of the thermoplastic foam composition.

[0098] In addition, still referring to Table 3, the flammability level burning rate measured according to test method FMVSS No. 302 shows that the encapsulation of unactivated biomass-based carbonaceous particulate material significantly improves the flame retardancy of the thermoplastic foam composition. More specifically, tests 1-4 show self-extinguishing properties. The flammability level burning rate of test 5 is less than 40 mm / min. Compared with the control 1 with a flammability level burning rate of 74 mm / min, and compared with the control 2 with a flammability level burning rate of 47 mm / min, it is obvious that tests 1-5 all show a significant improvement in flame retardancy. Such a result is unexpected because the basic unactivated biomass-based carbonaceous particulate material - and the biomass derived therefrom (e.g., wood) - is easy to catch fire. In addition, flame retardancy is particularly important in the final product of automotive applications (such as seat structures).

[0099] Table 1

[0100]

[0101] Table 2

[0102]

[0103]

[0104] Table 3

[0105]

[0106]

[0107] The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of words of description rather than limitation. Numerous modifications and variations of the present invention are possible in light of the above teachings, and the present invention may be practiced in ways other than those specifically described.

Claims

1. A thermoplastic foam composition for low-density and high-rigidity articles, the thermoplastic foam composition comprising: Thermoplastic foams; and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam; wherein the thermoplastic foam composition has a core density between 12 g / L and 400 g / L as measured according to ASTM-D3575-W Test Method A, and wherein the thermoplastic foam composition has an elastic modulus between 60 psi and 3500 psi measured according to ASTM-C203 Method I, Equation 13.

2. The thermoplastic foam composition according to claim 1, wherein the specific surface area of ​​the unactivated biomass-based carbon-containing particulate material is between 150 square meters per gram of the unactivated biomass-based carbon-containing particulate material and 495 square meters per gram of the unactivated biomass-based carbon-containing particulate material.

3. The thermoplastic foam composition according to any one of claims 1 and 2, wherein the specific surface area of ​​the unactivated biomass-based carbon-containing particulate material is between 190 square meters per gram of the unactivated biomass-based carbon-containing particulate material and 495 square meters per gram of the unactivated biomass-based carbon-containing particulate material.

4. The thermoplastic foam composition of any one of claims 1-3, wherein the unactivated biomass-based carbonaceous particulate material comprises 0.1 wt% to 25 wt% of the thermoplastic foam composition.

5. The thermoplastic foam composition of any one of claims 1-4, wherein the unactivated biomass-based carbonaceous particulate material comprises 0.5 wt% to 20 wt% of the thermoplastic foam composition.

6. The thermoplastic foam composition of any one of claims 1-5, wherein the unactivated biomass-based carbonaceous particulate material is uniformly distributed and dispersed throughout the thermoplastic foam.

7. The thermoplastic foam composition of any one of claims 1 to 6, wherein the unactivated biomass-based carbonaceous particulate material has a D50 particle size of 0.2 microns to 12.5 microns.

8. The thermoplastic foam composition of any one of claims 1-7, wherein the unactivated biomass-based carbonaceous particulate material has a D50 particle size of 1 micron to 8 microns.

9. The thermoplastic foam composition of any one of claims 1 to 8, wherein the unactivated biomass-based carbonaceous particulate material has a modern carbon percentage (pMC) greater than 75% as measured according to ASTM D6866.

10. The thermoplastic foam composition according to any one of claims 1 to 9, wherein the thermoplastic foam is further defined as an expanded thermoplastic foam formed by a blowing agent.

11. The thermoplastic foam composition of any one of claims 1 to 10, which is self-extinguishing and, other than the unactivated biomass-based carbonaceous particulate material, is free of flame retardants.

12. The thermoplastic foam composition of any one of claims 1-11, wherein the thermoplastic foam defines cells having a unimodal cell structure distribution.

13. The thermoplastic foam composition of claim 12, wherein the average size of the cells is less than 200 microns.

14. The thermoplastic foam composition of any one of claims 1-13, wherein the thermoplastic foam is substantially free of cell nucleating agents other than the unactivated biomass-based carbonaceous particulate material.

15. The thermoplastic foam composition of any one of claims 1-14, wherein the elastic modulus is at least 10% greater than the elastic modulus of a reference thermoplastic foam having the thermoplastic foam composition but omitting the unactivated biomass-based carbon-containing particulate material, as measured according to ASTM-C203 Method I, Equation 13.

16. The thermoplastic foam composition of claim 15, having a 25% strain compression set percentage measured according to ASTM-D3575-B that is within 25% of the 25% strain compression set percentage of the reference thermoplastic foam omitting the unactivated biomass-based carbonaceous particulate material.

17. The thermoplastic foam composition of any one of claims 15 and 16, having a flexural strength within 10% of the flexural strength of the reference thermoplastic foam omitting the unactivated biomass-based carbonaceous particulate material as measured according to ASTM-C203.

18. The thermoplastic foam composition of any one of claims 1-17, having a 50% strain compressive strength of at least 40 kilopascals as measured according to ASTM-D3575-D.

19. The thermoplastic foam composition of any one of claims 1-18, wherein the thermoplastic foam comprises expanded polypropylene.

20. The thermoplastic foam composition of claim 19, wherein the expanded polypropylene comprises at least 50 wt% of a copolymer of polypropylene and 5 wt% to 30 wt% of an ethylene-propylene rubber.

21. The thermoplastic foam composition of claim 19, wherein the expanded polypropylene comprises an expanded ethylene propylene 1-butene terpolymer.

22. The thermoplastic foam composition of any one of claims 19-21, wherein the expanded polypropylene has a core density between 12 g / L and 68 g / L measured according to ASTM-D3575-W Test Method A.

23. The thermoplastic foam composition of any one of claims 1-21, wherein the core density is between 12 g / L and 68 g / L as measured according to ASTM-D3575-W Test Method A.

24. The thermoplastic foam composition according to any one of claims 1 to 18, wherein the thermoplastic foam comprises a thermoplastic elastomer obtained by polycondensation of a carboxylic acid polyamide and an alcohol-terminated polyether.

25. The thermoplastic foam composition of any one of claims 1-18, wherein the thermoplastic foam comprises a thermoplastic polyurethane.

26. A thermoplastic polyurethane foam composition for low-density and high-rigidity articles, the thermoplastic polyurethane foam composition comprising: Thermoplastic polyurethane foam; and a biomass-based carbonaceous particulate material encapsulated in the thermoplastic polyurethane foam; wherein the thermoplastic polyurethane foam composition has a core density between 80 g / L and 400 g / L as measured according to ASTM-D3575-W Test Method A, and wherein the thermoplastic polyurethane foam composition has an elastic modulus between 60 psi and 700 psi measured according to ASTM-C203 Method I, Equation 13.

27. The thermoplastic polyurethane foam composition of claim 26, wherein the specific surface area of ​​the biomass-based carbon-containing particulate material is between 150 m2 / g of the biomass-based carbon-containing particulate material and 2000 m2 / g of the biomass-based carbon-containing particulate material.

28. The thermoplastic polyurethane foam composition of claim 27, wherein the biomass-based carbon-containing particulate material is further defined as an unactivated biomass-based carbon-containing particulate material, and wherein the specific surface area of ​​the unactivated biomass-based carbon-containing particulate material is between 150 square meters per gram of the unactivated biomass-based carbon-containing particulate material and 495 square meters per gram of the unactivated biomass-based carbon-containing particulate material.

29. The thermoplastic polyurethane foam composition of claim 27, wherein the biomass-based carbon-containing particulate material is further defined as an activated biomass-based carbon-containing particulate material, and wherein the specific surface area of ​​the activated biomass-based carbon-containing particulate material is between 495 square meters per gram of the activated biomass-based carbon-containing particulate material and 2000 square meters per gram of the activated biomass-based carbon-containing particulate material.

30. The thermoplastic polyurethane foam composition of any one of claims 26-29, wherein the biomass-based carbon-containing particulate material comprises 0.1 wt% to 25 wt% of the thermoplastic polyurethane foam composition.

31. The thermoplastic polyurethane foam composition of any one of claims 26-30, wherein the biomass-based carbon-containing particulate material comprises 0.5 wt% to 20 wt% of the thermoplastic polyurethane foam composition.

32. The thermoplastic polyurethane foam composition of any one of claims 26-31, wherein the biomass-based carbon-containing particulate material is evenly distributed and dispersed throughout the thermoplastic polyurethane foam.

33. The thermoplastic polyurethane foam composition of any one of claims 26-32, wherein the biomass-based carbon-containing particulate material has a D50 particle size of 0.1 microns to 200 microns.

34. The thermoplastic polyurethane foam composition of any one of claims 26-33, wherein the biomass-based carbon-containing particulate material has a D50 particle size of 1 micron to 50 microns.

35. The thermoplastic polyurethane foam composition of any one of claims 26-34, wherein the biomass-based carbon-containing particulate material has a modern carbon percentage (pMC) greater than 75% as measured according to ASTM D6866.

36. The thermoplastic polyurethane foam composition of any one of claims 26-35, wherein the thermoplastic polyurethane foam is further defined as an expanded thermoplastic polyurethane foam formed by a blowing agent.

37. The thermoplastic polyurethane foam composition of any one of claims 26-36, which is self-extinguishing and, other than the biomass-based carbonaceous particulate material, is free of flame retardants.

38. The thermoplastic polyurethane foam composition of any one of claims 26-37, wherein the thermoplastic polyurethane foam defines cells having a unimodal cell structure distribution.

39. The thermoplastic polyurethane foam composition of claim 38, wherein the average size of the cells is less than 200 microns.

40. The thermoplastic polyurethane foam composition of any one of claims 26-39, wherein the thermoplastic polyurethane foam is substantially free of cell nucleating agents other than the biomass-based carbon-containing particulate material.

41. The thermoplastic polyurethane foam composition of any one of claims 26-40, wherein the elastic modulus is at least 10% greater than the elastic modulus of a reference thermoplastic polyurethane foam having the thermoplastic polyurethane foam composition but omitting the biomass-based carbon-containing particulate material, as measured according to ASTM-C203 Method I, Equation 13.

42. The thermoplastic polyurethane foam composition of claim 41, having a 25% strain compression set percentage measured according to ASTM-D3575-B that is within 25% of the 25% strain compression set percentage of the reference thermoplastic polyurethane foam omitting the biomass-based carbon-containing particulate material.

43. The thermoplastic polyurethane foam composition of any one of claims 41 and 42, having a flexural strength within 10% of the flexural strength of the reference thermoplastic polyurethane foam omitting the biomass-based carbon-containing particulate material as measured according to ASTM-C203.

44. The thermoplastic polyurethane foam composition of any one of claims 26-43 having a 50% strain compressive strength of at least 40 kilopascals as measured by ASTM-D3575-D.

45. The thermoplastic polyurethane foam composition of any one of claims 26-44 having a core density between 100 and 300 g / L as measured according to ASTM-D3575-W Test Method A.

46. ​​The thermoplastic polyurethane foam composition of any one of claims 26-45 having a core density between 150 and 250 g / L as measured according to ASTM-D3575-W Test Method A.

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