Thermoplastic foam composition containing biomass-based carbonaceous particulate matter

Abstract

The thermoplastic foam composition for low density and high rigidity 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 12 grams / liter to 400 grams / liter as measured according to ASTM-D3575-W test method A. The thermoplastic foam composition also has a modulus of elasticity of 60 pounds per square inch to 3500 pounds per square inch as measured according to ASTM-C203 method I, equation 13.

Description

Technical Field

[0001] Background of the Invention 1. Field of the Invention The present invention generally relates to a thermoplastic foam composition comprising biomass-based carbonaceous particulate matter.

[0002] 2. Description of the Related Art Foam compositions generally include a polymeric foam and additives encapsulated within the polymeric foam. One additive commonly encapsulated within the polymeric foam is carbon black. Carbon black is a colorant that imparts color to the polymeric foam and is an ultraviolet (UV) stabilizer that protects the polymeric foam from degradation resulting from exposure to ultraviolet energy. However, carbon black is a petroleum-based additive produced from the reaction of hydrocarbon fuels and air at high temperatures, and is therefore non-renewable, unsustainable, has a high global warming potential (GWP), and leaves a large carbon footprint. Accordingly, there remains a need to provide improved foam compositions.

[0003] Summary and Advantages of the Invention The present invention provides a thermoplastic foam composition for low density and high stiffness articles. The thermoplastic foam composition includes a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated within the thermoplastic foam. The thermoplastic foam composition has a core density of 12 grams per liter to 400 grams per liter as measured according to ASTM-D3575-W test method A. The thermoplastic foam composition also has a modulus of elasticity of 60 pounds per square inch to 3500 pounds per square inch as measured according to ASTM-C203 method I, equation 13.

[0004] The present invention also provides a thermoplastic polyurethane foam composition for low-density and high-rigidity articles. The thermoplastic polyurethane foam composition includes 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 of 12 grams / liter to 400 grams / liter as measured according to ASTM-D3575-W test method A. The thermoplastic polyurethane foam composition also has a modulus of elasticity of 60 pounds per square inch to 700 pounds per square inch as measured according to ASTM-C203 method I, equation 13.

[0005] The unactivated biomass-based carbonaceous particulate material and the biomass-based carbonaceous particulate material are non-petroleum-based additives, renewable resources, sustainable, have a low global warming potential (GWP), and leave a low carbon footprint. More specifically, the unactivated biomass-based carbonaceous particulate material and the biomass-based carbonaceous particulate material have a low carbon footprint because the biomass from which the unactivated biomass-based carbonaceous particulate material and the biomass-based carbonaceous particulate material are derived sequesters carbon dioxide from the atmosphere during its lifespan. Furthermore, the unactivated biomass-based carbonaceous particulate material and the biomass-based carbonaceous particulate material are suitable for encapsulation in the foam to provide a low-density article and are also suitable for adjusting the modulus of elasticity of the foam to provide a high-rigidity article.

[0006] Accordingly, certain features of embodiments of the present invention have been outlined in order that the detailed description thereof may be better understood, and in order that the contribution of the present invention to the art may be better appreciated. Additional or alternative features of embodiments of the present invention are described in further detail below.

Brief Description of the Drawings

[0007] Other advantages of the present invention will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings.

[0008]

Figure 1

[0009]

Figure 2

[0010]

Figure 3

[0011] Detailed Description of the Invention Referring to the drawings, a thermoplastic foam composition for low density and high rigidity articles is provided. The thermoplastic foam composition includes a thermoplastic foam and unactivated biomass-based carbonaceous particulate matter encapsulated in the thermoplastic foam. The thermoplastic foam composition has a core density of 12 grams / liter to 400 grams / liter as measured according to ASTM-D3575-W test method A. The thermoplastic foam composition also has a modulus of elasticity of 60 pounds per square inch to 3500 pounds per square inch as measured according to ASTM-C203 method I, equation 13.

[0012] The unactivated biomass-based carbonaceous particulate matter is a non-petroleum-based additive, a renewable resource, sustainable, has a low global warming potential (GWP), and leaves a low carbon footprint. More specifically, the unactivated biomass-based carbonaceous particulate matter has a low carbon footprint because the biomass from which the unactivated biomass-based carbonaceous particulate matter is derived sequesters carbon dioxide from the atmosphere during its lifetime. Further, the unactivated biomass-based carbonaceous particulate matter is suitable for encapsulation in a thermoplastic foam to provide a low-density article and, at the same time, is also suitable for adjusting the elastic modulus of the thermoplastic foam to provide a high-rigidity article. The unactivated biomass-based carbonaceous particulate matter may be a colorant that imparts color to the thermoplastic foam or may be an ultraviolet (UV) stabilizer that protects the thermoplastic foam from degradation resulting from exposure to ultraviolet energy.

[0013] The unactivated biomass-based carbonaceous particulate matter is derived from biomass raw materials that have undergone pyrolysis and includes, inter alia, trees, wood chips, and / or both leaves of coniferous and / or deciduous trees including the wood of Acer psuedoplatanus, a part of the leaves of the most common maple in Europe, tree materials (e.g., wood, wood chips, and / or leaves), nut shells (e.g., coconut shells, walnut shells, hazelnut shells, peanut shells, etc.), bamboo, rice husks, grass, corn stover, plant matter, seeds, paper, cardboard, fertilizers, other agricultural residues, biorefinery residues, sorghum, dried algae, coffee beans, coffee grounds, powders, sugarcane bagasse, and any combination thereof, but is not limited thereto.

[0014] The unactivated biomass-based carbonaceous particulate matter is untreated except for being derived from biomass raw materials that have undergone pyrolysis. In other words, the unactivated biomass-based carbonaceous particulate matter is not treated with steam or chemical treatment that activates the unactivated biomass-based carbonaceous particulate matter, improves the porosity of the unactivated biomass-based carbonaceous particulate matter, increases the specific surface area of the unactivated biomass-based carbonaceous particulate matter, and reduces the relative ash content of the unactivated biomass-based carbonaceous particulate matter. The steam or chemical treatment required to activate the unactivated biomass-based carbonaceous particulate matter increases the net carbon dioxide emissions of the thermoplastic foam composition, increases the carbon footprint, and increases the global warming potential. By using the unactivated biomass-based carbonaceous particulate matter, the carbon dioxide emissions are reduced by about 2.5 pounds of carbon dioxide per pound of the unactivated biomass-based carbonaceous particulate matter compared to the activated biomass-based carbonaceous particulate matter.

[0015] The unactivated biomass-based carbonaceous particulate matter is porous. The porosity of the unactivated biomass-based carbonaceous particulate matter 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 unactivated biomass-based carbonaceous particulate matter may be 50% - 90%, 60% - 80%, 65% - 75%, or about 70%. It should be understood that the porosity of the unactivated biomass-based carbonaceous particulate matter varies depending on the specific biomass from which the unactivated biomass-based carbonaceous particulate matter is derived.

[0016] The unactivated biomass-based carbonaceous particulate matter may have a specific surface area of 150 square meters per gram to 495 square meters per gram of the unactivated biomass-based carbonaceous particulate matter. The unactivated biomass-based carbonaceous particulate matter may have a specific surface area of 190 square meters per gram to 495 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, 200 square meters per gram to 485 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, 250 square meters per gram to 485 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, 300 square meters per gram to 485 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, 200 square meters per gram to 450 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, 200 square meters per gram to 400 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, 200 square meters per gram to 350 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, or 200 square meters per gram to 300 square meters per gram of the unactivated biomass-based carbonaceous particulate matter.

[0017] The unactivated biomass-based carbonaceous particulate matter may be 0.1 wt% to 25 wt% of the thermoplastic foam composition. Further, the unactivated biomass-based carbonaceous particulate matter may be 0.5 wt% to 20 wt% of the thermoplastic foam composition, 0.5 wt% to 15 wt% of the thermoplastic foam composition, 0.5 wt% to 12 wt% of the thermoplastic foam composition, 0.5 wt% to 10 wt% of the thermoplastic foam composition, 0.5 wt% to 8 wt% of the thermoplastic foam composition, 0.5 wt% to 6 wt% of the thermoplastic foam composition, 0.5 wt% to 5 wt% of the thermoplastic foam composition, 0.5 wt% to 4 wt% of the thermoplastic foam composition, 0.5 wt% to 3 wt% of the thermoplastic foam composition, 0.5 wt% to 2 wt% of the thermoplastic foam composition, or 0.5 wt% to 1 wt% of the thermoplastic foam composition. Further, the unactivated biomass-based carbonaceous particulate matter may be 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.

[0018] Furthermore, the unactivated biomass-based carbonaceous particulate matter may be 2 wt% to 20 wt%, 2 wt% to 15 wt%, 2 wt% to 12 wt%, 2 wt% to 10 wt%, 2 wt% to 8 wt%, 2 wt% to 6 wt%, 2 wt% to 5 wt%, 2 wt% to 4 wt%, and 2 wt% to 3 wt% of the thermoplastic foam composition. Furthermore, the unactivated biomass-based carbonaceous particulate matter may be 3 wt% to 20 wt%, 3 wt% to 15 wt%, 3 wt% to 12 wt%, 3 wt% to 10 wt%, 3 wt% to 8 wt%, 3 wt% to 6 wt%, 3 wt% to 5 wt%, and 3 wt% to 4 wt% of the thermoplastic foam composition.

[0019] It should be understood that the unactivated biomass-based carbonaceous particulate matter may be more than 20 wt% of the thermoplastic foam composition. Although not essential, the thermoplastic foam is typically petroleum-based. It should be understood that the unactivated biomass-based carbonaceous particulate matter replaces the thermoplastic foam in terms of the relative weight percentage in the thermoplastic foam composition. Thus, the higher the weight percentage of the unactivated biomass-based carbonaceous particulate matter in the thermoplastic foam composition, the lower the relative weight percentage of the thermoplastic foam in the thermoplastic foam composition, and thus the further reduction of the carbon footprint of the thermoplastic foam composition.

[0020] Even if the weight percentage of the unactivated biomass-based carbonaceous particulate matter in the thermoplastic foam composition is high, the melt pressure does not increase, and when processed in an extruder, the extruder torque does not increase. Thus, encapsulation of the unactivated biomass-based carbonaceous particulate matter into the thermoplastic foam composition does not increase the energy consumption during extrusion. Also, encapsulation of the unactivated biomass-based carbonaceous particulate matter into the thermoplastic foam had little or no significant effect on the viscosity or rheological behavior of the thermoplastic foam.

[0021] As shown in FIGS. 1 to 3, the unactivated biomass-based carbonaceous particulate matter may be uniformly distributed and dispersed throughout the thermoplastic foam. It should be understood that FIGS. 1 to 3 are images taken by a scanning electron microscope (SEM) of the thermoplastic foam composition. The unactivated biomass-based carbonaceous particulate matter is uniformly distributed throughout the thermoplastic foam such that any given portion of the thermoplastic foam composition has approximately the same concentration of unactivated biomass-based carbonaceous particulate matter. Further, the unactivated biomass-based carbonaceous particulate matter has a D50 particle size, and the D50 particle size may have a unimodal particle size distribution such that the unactivated biomass-based particulate matter is uniformly dispersed throughout the thermoplastic foam. In other words, the unactivated biomass-based carbonaceous particulate matter does not contain aggregates that would produce a bimodal particle size distribution.

[0022] The unactivated biomass-based carbonaceous particulate matter can have a D50 particle size of 0.1 micron to 200 microns. The D50 particle size represents the average diameter of the unactivated biomass-based carbonaceous particulate matter as measured according to ISO 13320. Further, the unactivated biomass-based carbonaceous particulate matter can have a D50 particle size of 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. Further, the unactivated biomass-based carbonaceous particulate matter can have a D50 particle size of 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 unactivated biomass-based carbonaceous particulate matter can even have an average diameter of less than 1 micron or greater than 100 microns.

[0023] The unactivated biomass-based carbonaceous particulate matter can also have a non-uniform particle size in the range of 1 micron to 50 microns, 1 micron to 35 microns, or 2 microns to 25 microns. Further, the unactivated biomass-based carbonaceous particulate matter can have a D50 particle size of 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 the particle size of the unactivated biomass-based carbonaceous particulate matter, the more likely the fusion property of the thermoplastic foam composition is to be improved.

[0024] The unactivated biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 75% as measured according to ASTM D6866. It should be understood that the unactivated biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 75%. As a non-limiting example, the unactivated biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 80% as measured according to ASTM D6866, the unactivated biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 85% as measured according to ASTM D6866, the unactivated biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 90% as measured according to ASTM D6866, the unactivated biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 95% as measured according to ASTM D6866, and the unactivated biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of about 100% as measured according to ASTM D6866. In a non-limiting example, the unactivated biomass-based carbonaceous particulate matter has a proportion of modern carbon (pMC) of more than 75%, an ash content of less than 12%, and a nitrogen level of less than 2%.

[0025] The thermoplastic foam can be further defined as a foamed thermoplastic foam formed via a blowing agent. The foamed thermoplastic foam can be formed by foaming using a blowing agent in an autoclave. However, it should also be understood that the thermoplastic foam can be formed directly by extrusion with an extruder.

[0026] The thermoplastic foam composition may be self - extinguishing. Further, although not essential, the thermoplastic foam composition preferably does not contain a flame retardant other than the unactivated biomass - based carbonaceous particulate material. The unactivated biomass - based carbonaceous particulate material is itself flammable, but the thermoplastic foam composition containing the thermoplastic foam and the unactivated biomass - based carbonaceous particulate material has been found to exhibit a flame - retardant effect. As a non - limiting example, a molded article having a core density of 18 grams / liter and 5 weight percent of the unactivated biomass - based carbonaceous particulate material has been found to be self - extinguishing. The thermoplastic foam composition may also be non - conductive to electricity.

[0027] As shown in FIGS. 1 - 3, the thermoplastic foam can define cells having a unimodal cell structure distribution. The unimodal cell structure distribution results in a uniform cell structure that aids in maintaining the dimensional stability and mechanical properties of the thermoplastic foam composition. By encapsulating the unactivated biomass - based carbonaceous particulate material in the thermoplastic foam, it has been found that a unimodal cell structure distribution is generated, a uniform cell structure is obtained, and at the same time, the average size of the cells is restricted.

[0028] The cells can 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. Restricting the average size of the cells further aids in maintaining the dimensional stability and mechanical properties of the thermoplastic foam composition. In addition, the cells can 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.

[0029] The thermoplastic foam may not substantially contain a cell nucleating agent other than the unactivated biomass-based carbonaceous particulate material. The thermoplastic foam may substantially not contain a cell nucleating agent by containing less than 1% by weight of the cell nucleating agent. The unactivated biomass-based carbonaceous particulate material can act as a cell nucleating agent for both isothermal crystallization and cell growth. However, it is clear that the unactivated biomass-based carbonaceous particulate material is not too strong as a cell nucleating agent such as other additives (e.g., talc) that prevent cell expansion and prevent the formation of a low-density thermoplastic foam composition. Furthermore, the unactivated biomass-based carbonaceous particulate material can promote cell nucleation but may prevent the growth of cells during foaming. Therefore, since the unactivated biomass-based carbonaceous particulate material is solid and does not actively contribute to the expansion during foaming, the thermoplastic foam composition having both low density and high rigidity was a remarkable achievement.

[0030] As described herein, the thermoplastic foam composition has a core density of 12 grams per liter to 400 grams per liter as measured according to ASTM-D3575-W test method A. The thermoplastic foam composition may also have a core density of 12 grams per liter to 300 grams per liter, 12 grams per liter to 250 grams per liter, 12 grams per liter to 200 grams per liter, 12 grams per liter to 150 grams per liter, 12 grams per liter to 100 grams per liter, 12 grams per liter to 80 grams per liter, 12 grams per liter to 68 grams per liter, 12 grams per liter to 67.3 grams per liter, and 12 grams per liter to 45 grams per liter. The core densities listed herein are examples of low-density articles.

[0031] Also, as described herein, the thermoplastic foam composition has a modulus of elasticity of 60 pounds per square inch to 3500 pounds per square inch as measured according to ASTM-C203 Method I, Equation 13. The thermoplastic foam composition may also have a modulus of elasticity of 60 pounds per square inch to 2500 pounds per square inch, 60 pounds per square inch to 2000 pounds per square inch, 60 pounds per square inch to 1000 pounds per square inch, 200 pounds per square inch to 2200 pounds per square inch, 250 pounds per square inch to 3500 pounds per square inch, 500 pounds per square inch to 3500 pounds per square inch, 600 pounds per square inch to 3500 pounds per square inch, 1000 pounds per square inch to 3500 pounds per square inch, 240 pounds per square inch to 2100 pounds per square inch, 300 pounds per square inch to 2100 pounds per square inch, 400 pounds per square inch to 2000 pounds per square inch, 400 pounds per square inch to 1500 pounds per square inch, 400 pounds per square inch to 1000 pounds per square inch, 400 pounds per square inch to 800 pounds per square inch, or about 600 pounds per square inch. It should be understood that the thermoplastic foam composition can have a modulus of elasticity of at least 600 pounds per square inch, preferably at least 700 pounds per square inch.

[0032] The elastic modulus of the thermoplastic foam composition, measured according to ASTM-C203 Method I, Equation 13, may be at least 10% greater than the elastic modulus of a reference thermoplastic foam having the thermoplastic foam of the thermoplastic foam composition but not containing the unactivated biomass-based carbonaceous particulate material. As described herein, encapsulation of the unactivated biomass-based carbonaceous particulate material increases the elastic modulus of the thermoplastic foam composition and thus cures the thermoplastic foam composition. The elastic modulus of the thermoplastic foam composition may also be at least 15% greater than the elastic modulus of a reference thermoplastic foam having the thermoplastic foam of the thermoplastic foam composition but not containing the unactivated biomass-based carbonaceous particulate material, 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 reference thermoplastic foam having the thermoplastic foam of the thermoplastic foam composition but not containing the unactivated biomass-based carbonaceous particulate material, measured according to ASTM-C203 Method I, Equation 13.

[0033] Furthermore, the unactivated biomass-based carbonaceous particulate material improves the elastic modulus of the thermoplastic foam composition while improving or maintaining other desirable mechanical properties of the thermoplastic foam composition as compared to typical thermoplastic foams containing carbon black. Adding additives to typical thermoplastic foams often has a significant adverse effect on the mechanical properties of the typical thermoplastic foams. However, it has unexpectedly been found that encapsulating the unactivated biomass-based carbonaceous particulate material maintains these other desirable mechanical properties.

[0034] As a non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition, measured according to ASTM-D3575-B, may have a compression set rate at 25% strain within 25% of a reference thermoplastic foam not containing the unactivated biomass-based carbonaceous particulate material. The thermoplastic foam composition may also have a compression set rate at 25% strain within 20%, 15%, 10%, or even 5% of a reference thermoplastic foam not containing the unactivated biomass-based carbonaceous particulate material, measured according to ASTM-D3575-B.

[0035] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition can have a flexural strength within 10% of the flexural strength of a reference thermoplastic foam that does not contain unactivated biomass-based carbonaceous particulate matter, as measured according to ASTM-C203. The thermoplastic foam composition can also have a flexural strength within 5% of the flexural strength of a reference thermoplastic foam that does not contain unactivated biomass-based carbonaceous particulate matter, as measured according to ASTM-C203. The flexural strength of the thermoplastic foam composition can be from 5 pounds per square inch to 125 pounds per square inch, from 5 pounds per square inch to 60 pounds per square inch, from 6 pounds per square inch to 110 pounds per square inch, from 6 pounds per square inch to 80 pounds per square inch, from 6 pounds per square inch to 50 pounds per square inch, from 7 pounds per square inch to 40 pounds per square inch, from 8 pounds per square inch to 50 pounds per square inch, from 8 pounds per square inch to 30 pounds per square inch, from 9 pounds per square inch to 25 pounds per square inch, and from 10 pounds per square inch to 20 pounds per square inch.

[0036] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition can have a compressive strength at 50% strain of at least 40 kilopascals, as measured according to ASTM-D3575-D. The thermoplastic foam composition can also have a compressive strength at 50% strain of at least 60 kilopascals, at least 80 kilopascals, at least 100 kilopascals, at least 150 kilopascals, at least 200 kilopascals, or at least 250 kilopascals, as measured according to ASTM-D3575-D. The thermoplastic foam composition can further have a compressive strength at 50% strain of at least 300 kilopascals, as measured according to ASTM-D3575-D. The thermoplastic foam composition has a compressive strength at 50% strain of 40 kilopascals to 4100 kilopascals, 60 kilopascals to 3000 kilopascals, 100 kilopascals to 2000 kilopascals, 150 kilopascals to 1000 kilopascals, 200 kilopascals to 600 kilopascals, 250 kilopascals to 400 kilopascals, 300 kilopascals to 350 kilopascals, about 300 kilopascals, about 325 kilopascals, or about 350 kilopascals.

[0037] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition has a compressive strength at 75% strain of 200 kilopascals to 13500 kilopascals, 310 kilopascals to 10000 kilopascals, 310 kilopascals to 5000 kilopascals, 310 kilopascals to 3000 kilopascals, 310 kilopascals to 2000 kilopascals, 310 kilopascals to 1000 kilopascals, 400 kilopascals to 800 kilopascals, 600 kilopascals to 800 kilopascals, 650 kilopascals to 750 kilopascals, or about 700 kilopascals.

[0038] As another non-limiting example of the mechanical properties of the thermoplastic foam composition, the thermoplastic foam composition has a tensile strength of 200 kilopascals to 2,800 kilopascals, 200 to 650 kilopascals, 260 kilopascals to 2,000 kilopascals, 260 kilopascals to 1,500 kilopascals, 300 kilopascals to 1,000 kilopascals, 400 kilopascals to 800 kilopascals, 500 kilopascals to 700 kilopascals, 550 kilopascals to 650 kilopascals, or about 600 kilopascals.

[0039] 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%.

[0040] The thermoplastic foam may include a thermoplastic polyolefin (TPO) such as a polyalkylene, including both linear polymers, branched polymers, or combinations thereof. Although not essential, the thermoplastic foam may include expanded polypropylene (EPP). The expanded polypropylene may be at least one selected from an expanded polypropylene homopolymer, an expanded polypropylene (random or block) copolymer, and an expanded polypropylene terpolymer. In other words, the thermoplastic foam may be an expanded polypropylene homopolymer, an expanded polypropylene copolymer, an expanded polypropylene terpolymer, or a combination thereof. In a non-limiting example, the thermoplastic foam may be a high-density expanded polypropylene (HDPP), a medium-density expanded polypropylene, or a low-density expanded polypropylene (LDPP). Although not essential, a higher weight percentage of unactivated biomass-based carbonaceous particulate matter may be used in high-density polypropylene compared to low-density polypropylene.

[0041] In embodiments where the thermoplastic foam is either a foamed polypropylene copolymer or a foamed polypropylene terpolymer, the thermoplastic foam may include propylene monomer units and at least one selected from ethylene monomer units, butylene monomer units, or other α-olefin monomer units. As a non-limiting example, the foamed polypropylene terpolymer may be a foamed ethylene propylene 1-butylene terpolymer.

[0042] In embodiments where the foamed polypropylene includes propylene monomer units, at least one of ethylene monomer units and butylene monomer units, and other α-olefin monomer units, the propylene monomer units, ethylene monomer units, butylene 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, butylene monomer units, and / or other α-olefin monomer units may have either a random or regular repeating pattern in the carbon backbone of the foamed polymer. Further, the tacticity of the propylene monomer units, ethylene monomer units, butylene monomer units, and / or other α-olefin monomer units may be such that the repeating monomer units are arranged in an atactic arrangement lacking regularity or coordination in their stereochemical orientation in the carbon backbone of the foamed polymer, the repeating monomer units may be arranged in a syndiotactic arrangement having regular alternations of different stereochemical orientations in the carbon backbone of the foamed polymer, or all of the repeating monomer units may be arranged in an isotactic arrangement having the same stereochemical orientation in the carbon backbone of the foamed polymer. It should be understood that a foamed polypropylene homopolymer may also be arranged in any of an atactic, syndiotactic, or isotactic arrangement.

[0043] The foamed polypropylene may contain a random copolymer of at least 50% by weight of polypropylene and 5% to 30% by weight of ethylene propylene rubber. The foamed polypropylene may contain a polyolefin elastomer and / or plastomer, such as Engage (trademark) manufactured by Dow. The foamed polypropylene may be a recycled material or an unused material. The foamed polypropylene may have a core density of 12 grams / liter to 68 grams / liter as measured according to ASTM-D3575-W test method A. Further, the foamed polypropylene may have a core density of 16 grams / liter to 68 grams / liter as measured according to ASTM-D3575-W test method A, or may have a core density of 12 grams / liter to 67.3 grams / liter as measured according to ASTM-D3575-W test method A, or may have a core density of 16 grams / liter to 50 grams / liter as measured according to ASTM-D3575-W test method A, or may have a core density of 16 grams / liter to 45 grams / liter as measured according to ASTM-D3575-W test method A, or may have a core density of 20 grams / liter to 45 grams / liter as measured according to ASTM-D3575-W test method A. The core densities listed herein are examples of low-density articles.

[0044] Furthermore, the thermoplastic foam may contain 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 nylon 6 (PA6), nylon 11 (PA11), and nylon 12 (PA12), but is not limited thereto, and the alcohol-terminated polyether may be polytetramethylene glycol (PTMG) or polyethylene glycol (PEG), but is not limited thereto.

[0045] As disclosed in this specification, the thermoplastic foam may be a polyolefin such as foamed polypropylene. It is also conceivable that the thermoplastic foam may 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 copolymer, stereoblock polypropylene, olefin block copolymer, propylene-butane copolymer, ethylene vinyl acetate copolymer (EVA), polyolefin elastomer (POE), or poly(α-olefin). However, the thermoplastic foam does not necessarily have to contain a polyolefin (e.g., foamed polypropylene).As a non-limiting example, the thermoplastic foam can be thermoplastic polyurethane (TPU), polyamide (PA), such as nylon, polymethylpentene (PMP), polyisobutylene (PIB), styrene-butadiene block copolymer and the hydrogenated products thereof, polyester (including but not limited to polyethylene terephthalate (PET) and polybutylene terephthalate (PBT)), polycarbonate (PC), bioplastic (including but not limited to polylactic acid and polylactide (PLA)), polybutylene adipate terephthalate (PBAT), poly(butylene succinate-co-butylene adipate) (PBSA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), poly(3-hydroxybutyrate) (PHBH), poly(p-phenylene oxide) or poly(p-phenylene ether) (PPE) (including blends with polystyrene or impact-resistant styrene-butadiene copolymer or polyamide), styrene polymer, such as polystyrene, expandable polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), and acrylonitrile-styrene-acrylate copolymer (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 copolymer (SBC), methyl methacrylate-butadiene-styrene (MBS), and styrene-ethylene-butylene-styrene (SEBS) may also be considered.

[0046] 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, for example, additional colorants, stabilizers such as ultraviolet 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). Further, the thermoplastic foam composition may include a resin useful for improving the foaming of the thermoplastic foam composition and / or a coupling agent for better mixing and dispersion.

[0047] Also provided herein are thermoplastic polyurethane foam compositions for low density and high rigidity articles. The thermoplastic polyurethane foam composition includes a thermoplastic polyurethane foam and a biomass-based carbonaceous particulate material encapsulated within the thermoplastic polyurethane foam. The thermoplastic polyurethane foam composition has a core density of 80 grams per liter to 400 grams per liter as measured according to ASTM-D3575-W test method A. The thermoplastic polyurethane foam composition also has a modulus of elasticity of 60 pounds per square inch to 700 pounds per square inch as measured according to ASTM-C203 method I, equation 13.

[0048] The biomass-based carbonaceous particulate material is a non-petroleum-based additive, a renewable resource, sustainable, has a low global warming potential (GWP), and leaves a low carbon footprint. More specifically, the biomass-based carbonaceous particulate material has a low carbon footprint because the biomass from which the biomass-based carbonaceous particulate material is derived sequesters carbon dioxide from the atmosphere during its lifetime. Further, the biomass-based carbonaceous particulate material is suitable for encapsulation into a foam for providing a low density article and is also suitable for adjusting the modulus of elasticity of the foam for providing a high rigidity article. The biomass-based carbonaceous particulate material may be a colorant that imparts color to the thermoplastic polyurethane foam or may be an ultraviolet (UV) stabilizer that protects the thermoplastic polyurethane foam from degradation resulting from exposure to ultraviolet energy.

[0049] The biomass-based carbonaceous particulate matter is derived from biomass raw materials that have undergone pyrolysis, and includes, in particular, trees, wood chips, and / or both leaves of trees such as maple trees, more specifically, a part of the leaves of the most common maple tree in Europe, Acer psuedoplatanus, tree materials (e.g., wood, wood chips, and / or leaves) from coniferous and / or deciduous trees, nut shells (e.g., coconut shells, walnut shells, hazelnut shells, peanut shells, etc.), bamboo, rice husks, grass, corn stover, plant matter, seeds, paper, cardboard, fertilizers, other agricultural residues, biorefinery residues, sorghum, dried algae, coffee beans, coffee grounds, powder, sugarcane bagasse, and any combination thereof, but is not limited thereto.

[0050] The biomass-based carbonaceous particulate matter is porous. The porosity of the biomass-based carbonaceous particulate matter may be more than 50%, more than 55%, more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, or more than 95%. The porosity of the biomass-based carbonaceous particulate matter may be 50% - 90%, 60% - 80%, 65% - 75%, or about 70%. It should be understood that the porosity of the biomass-based carbonaceous particulate matter varies depending on the specific biomass from which the biomass-based carbonaceous particulate matter is derived.

[0051] In particular, in embodiments disclosing a thermoplastic polyurethane foam composition, the biomass-based carbonaceous particulate matter need not be unactivated. Instead, both activated biomass-based carbonaceous particulate matter and unactivated biomass-based carbonaceous particulate matter are considered suitable for encapsulation into the thermoplastic polyurethane foam. The biomass-based carbonaceous particulate matter may have a specific surface area of 150 square meters per gram of biomass-based carbonaceous particulate matter to 2000 square meters per gram of biomass-based carbonaceous particulate matter.

[0052] The biomass-based carbonaceous particulate matter may be further defined as unactivated biomass-based carbonaceous particulate matter, and the unactivated biomass-based carbonaceous particulate matter may have a specific surface area of 150 square meters per gram to 495 square meters per gram of the unactivated biomass-based carbonaceous particulate matter. The unactivated biomass-based carbonaceous particulate matter may have a specific surface area of 190 square meters per gram to 495 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, may have a specific surface area of 200 square meters per gram to 450 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, may have a specific surface area of 200 square meters per gram to 400 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, may have a specific surface area of 200 square meters per gram to 350 square meters per gram of the unactivated biomass-based carbonaceous particulate matter, or may have a specific surface area of 200 square meters per gram to 300 square meters per gram of the unactivated biomass-based carbonaceous particulate matter.

[0053] Alternatively, the biomass-based carbonaceous particulate matter may be further defined as activated biomass-based carbonaceous particulate matter, which has a specific surface area of 495 square meters per gram to 2000 square meters per gram of the activated biomass-based carbonaceous particulate matter. The activated biomass-based carbonaceous particulate matter may have a specific surface area of 495 square meters per gram to 1500 square meters per gram, 495 square meters per gram to 1200 square meters per gram, or 495 square meters per gram to 1000 square meters per gram of the activated biomass-based carbonaceous particulate matter. The activated biomass-based carbonaceous particulate matter is treated by steam and / or chemical treatment, etc.

[0054] Furthermore, the thermoplastic polyurethane foam composition may be recyclable. The thermoplastic polyurethane foam composition may contain crosslinks, but these crosslinks are not to the extent that the thermoplastic polyurethane foam is a thermosetting material.

[0055] The biomass-based carbonaceous particulate matter may be 0.1% to 25% by weight of the thermoplastic polyurethane foam composition. Further, the biomass-based carbonaceous particulate matter may be 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. Further, the biomass-based carbonaceous particulate matter may be 1% to 20% by weight of the thermoplastic polyurethane foam composition, 1% to 15% by weight of the thermoplastic polyurethane foam composition, 1% to 12% by weight of the thermoplastic polyurethane foam composition, 1% to 10% by weight of the thermoplastic polyurethane foam composition, 1% to 8% by weight of the thermoplastic polyurethane foam composition, 1% to 6% by weight of the thermoplastic polyurethane foam composition, 1% to 5% by weight of the thermoplastic polyurethane foam composition, 1% to 4% by weight of the thermoplastic polyurethane foam composition, 1% to 3% by weight of the thermoplastic polyurethane foam composition, and 1% to 2% by weight of the thermoplastic polyurethane foam composition.

[0056] Furthermore, the biomass-based carbonaceous particulate matter may be 2% to 20% by weight, 2% to 15% by weight, 2% to 12% by weight, 2% to 10% by weight, 2% to 8% by weight, 2% to 6% by weight, 2% to 5% by weight, 2% to 4% by weight, or 2% to 3% by weight of the thermoplastic polyurethane foam composition. Furthermore, the biomass-based carbonaceous particulate matter may be 3% to 20% by weight, 3% to 15% by weight, 3% to 12% by weight, 3% to 10% by weight, 3% to 8% by weight, 3% to 6% by weight, 3% to 5% by weight, or 3% to 4% by weight of the thermoplastic polyurethane foam composition.

[0057] It should be understood that the biomass-based carbonaceous particulate matter may be more than 20% by weight of the thermoplastic polyurethane foam composition. Although not essential, the thermoplastic polyurethane foam is typically petroleum-based. It should be understood that the biomass-based carbonaceous particulate matter can replace the thermoplastic polyurethane foam in terms of the relative weight percentage in the thermoplastic polyurethane foam composition. Thus, the higher the weight percentage of the biomass-based carbonaceous particulate matter in the thermoplastic polyurethane foam composition, the lower the relative weight percentage of the thermoplastic polyurethane foam in the thermoplastic polyurethane foam composition, and thus the lower the carbon footprint of the thermoplastic polyurethane foam composition.

[0058] Even when the weight percentage of the biomass-based carbonaceous particulate matter in the thermoplastic polyurethane foam composition is high, the melt pressure does not increase, and when processed with an extruder, the extruder torque does not increase. Thus, the incorporation of the biomass-based carbonaceous particulate matter in the thermoplastic polyurethane foam composition does not increase the energy consumption during extrusion. The incorporation of the biomass-based carbonaceous particulate matter in the thermoplastic polyurethane foam also had little or no significant effect on the viscosity or rheological behavior of the thermoplastic polyurethane foam.

[0059] The biomass-based carbonaceous particulate matter may be uniformly distributed and dispersed throughout the thermoplastic polyurethane foam. The biomass-based carbonaceous particulate matter is uniformly distributed throughout the thermoplastic polyurethane foam such that any given portion of the thermoplastic polyurethane foam composition has approximately the same concentration of the biomass-based carbonaceous particulate matter. Further, the biomass-based carbonaceous particulate matter has a D50 particle size, and the D50 particle size may have a unimodal particle size distribution such that the biomass-based particulate matter is uniformly dispersed throughout the thermoplastic polyurethane foam. In other words, the biomass-based carbonaceous particulate matter does not contain aggregates that give rise to a bimodal particle size distribution.

[0060] The biomass-based carbonaceous particulate matter may have a D50 particle size of 0.1 micron to 200 microns. The D50 particle size represents the average diameter of the biomass-based carbonaceous particulate matter measured in accordance with ISO 13320. Further, the biomass-based carbonaceous particulate matter may have a D50 particle size of 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. Further, the biomass-based carbonaceous particulate matter may have a D50 particle size of 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 biomass-based carbonaceous particulate matter may even have an average diameter of less than 1 micron or more than 100 microns.

[0061] The biomass-based carbonaceous particulate matter may also have a non-uniform particle size in the range of 1 micron to 50 microns, 1 micron to 35 microns, or 2 microns to 25 microns. Further, the biomass-based carbonaceous particulate matter may have a D50 particle size of 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 the particle size of the biomass-based carbonaceous particulate matter, the more the fusion property of the thermoplastic polyurethane foam composition tends to improve.

[0062] Biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 75% as measured according to ASTM D6866. It should be understood that biomass-based carbonaceous particulate matter can have a proportion of modern carbon (pMC) of more than 75%. As a non-limiting example, biomass-based carbonaceous particulate matter may have a proportion of modern carbon (pMC) of more than 80% as measured according to ASTM D6866, biomass-based carbonaceous particulate matter may have a proportion of modern carbon (pMC) of more than 85% as measured according to ASTM D6866, biomass-based carbonaceous particulate matter may have a proportion of modern carbon (pMC) of more than 90% as measured according to ASTM D6866, biomass-based carbonaceous particulate matter may have a proportion of modern carbon (pMC) of more than 95% as measured according to ASTM D6866, and biomass-based carbonaceous particulate matter may have a proportion of modern carbon (pMC) of about 100% as measured according to ASTM D6866. In a non-limiting example, biomass-based carbonaceous particulate matter has a proportion of modern carbon (pMC) of more than 75%, an ash content of less than 12%, and a nitrogen level of less than 2%.

[0063] The thermoplastic polyurethane foam can be further defined as a foamed thermoplastic polyurethane foam formed via a blowing agent. The foamed thermoplastic polyurethane foam can be formed by foaming using a blowing agent in an autoclave. However, it should also be understood that the thermoplastic polyurethane foam can be directly formed by extrusion using an extruder.

[0064] The thermoplastic polyurethane foam composition may be self-extinguishing. Further, although not essential, the thermoplastic polyurethane foam composition preferably does not contain a flame retardant other than the biomass-based carbonaceous particulate matter. The biomass-based carbonaceous particulate matter is itself flammable, but a thermoplastic polyurethane foam composition containing the thermoplastic polyurethane foam and the biomass-based carbonaceous particulate matter has been found to exhibit a flame retardant effect. The thermoplastic polyurethane foam composition may also be non-conductive to electricity.

[0065] The thermoplastic polyurethane foam can define cells having a unimodal cell structure distribution. The unimodal cell structure distribution results in a uniform cell structure and helps maintain the dimensional stability and mechanical properties of the thermoplastic polyurethane foam composition. By encapsulating biomass-based carbonaceous particulate matter in the thermoplastic polyurethane foam, it has been found that a unimodal cell structure distribution is generated, resulting in a uniform cell structure and at the same time restricting the average cell size.

[0066] The cells can 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. Restricting the average cell size further aids in maintaining the dimensional stability and mechanical properties of the thermoplastic polyurethane foam composition. Further, the cells can 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.

[0067] The thermoplastic polyurethane foam may not contain a cell nucleating agent other than the biomass-based carbonaceous particulate matter. The thermoplastic polyurethane foam may substantially not contain a cell nucleating agent by containing less than 1 wt% of the cell nucleating agent. The biomass-based carbonaceous particulate matter can act as a nucleating agent for both isothermal crystallization and cell growth. However, it is clear that the biomass-based carbonaceous particulate matter is not too strong as a cell nucleating agent like other additives (e.g., talc) that hinder cell expansion and the formation of a low-density thermoplastic polyurethane foam composition. Further, the biomass-based carbonaceous particulate matter can promote cell nucleation but may hinder cell growth during foaming. Therefore, since the biomass-based carbonaceous particulate matter is solid and does not actively contribute to the expansion during foaming, the thermoplastic polyurethane foam composition having both low density and high rigidity has been a remarkable achievement.

[0068] As described herein, the thermoplastic polyurethane foam composition has a core density of 80 grams per liter to 400 grams per liter as measured according to ASTM-D3575-W test method A. The thermoplastic polyurethane foam composition may also have a core density of 100 grams per liter to 300 grams per liter, 150 grams per liter to 250 grams per liter, 100 grams per liter to 200 grams per liter, and 100 grams per liter to 150 grams per liter. The core densities listed herein are examples of low-density articles.

[0069] Also, as described herein, the thermoplastic polyurethane foam composition has a modulus of elasticity of 60 pounds per square inch to 700 pounds per square inch as measured according to ASTM-C203 method I, equation 13. The thermoplastic polyurethane foam composition may also have a modulus of elasticity of 60 pounds per square inch to 500 pounds per square inch, 80 pounds per square inch to 400 pounds per square inch, 100 pounds per square inch to 350 pounds per square inch, or 150 pounds per square inch to 300 pounds per square inch. It should be understood that the thermoplastic polyurethane foam composition can have a modulus of elasticity of at least 100 pounds per square inch.

[0070] The elastic modulus of the thermoplastic polyurethane foam composition is measured according to ASTM-C203 Method I, Equation 13, and may be at least 10% greater than the elastic modulus of a reference thermoplastic polyurethane foam having the thermoplastic polyurethane foam of the thermoplastic polyurethane foam composition but not containing the biomass-based carbonaceous particulate material. As described herein, the encapsulation of the biomass-based carbonaceous particulate material increases the elastic modulus of the thermoplastic polyurethane foam composition and thus cures the thermoplastic polyurethane foam composition. The elastic modulus of the thermoplastic polyurethane foam composition may also be at least 15% greater than the elastic modulus of a reference thermoplastic polyurethane foam having the thermoplastic polyurethane foam of the thermoplastic polyurethane foam composition but not containing the biomass-based carbonaceous particulate material, when 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 reference thermoplastic polyurethane foam having the thermoplastic polyurethane foam of the thermoplastic polyurethane foam composition but not containing the biomass-based carbonaceous particulate material, when measured according to ASTM-C203 Method I, Equation 13.

[0071] Furthermore, the biomass-based carbonaceous particulate material improves the elastic modulus of the thermoplastic polyurethane foam composition while maintaining other desirable mechanical properties of the thermoplastic polyurethane foam composition, as compared to a typical thermoplastic polyurethane foam containing carbon black. Often, the addition of additives to a typical thermoplastic polyurethane foam has a significant adverse effect on the mechanical properties of the typical thermoplastic polyurethane foam. However, it has unexpectedly been found that by encapsulating the biomass-based carbonaceous particulate material, these other desirable mechanical properties are maintained.

[0072] As a non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the thermoplastic polyurethane foam composition may have a compression set rate at 25% strain, as measured according to ASTM-D3575-B, within 25% of that of a reference thermoplastic polyurethane foam that does not contain biomass-based carbonaceous particulate matter. The thermoplastic polyurethane foam composition may also have a compression set rate at 25% strain, as measured according to ASTM-D3575-B, within 20%, within 15%, within 10%, or even within 5% of that of a reference thermoplastic polyurethane foam that does not contain biomass-based carbonaceous particulate matter.

[0073] As another non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the thermoplastic polyurethane foam composition may have a flexural strength within 10% of the flexural strength of a reference thermoplastic polyurethane foam that does not contain biomass-based carbonaceous particulate matter, as measured according to ASTM-C203. The thermoplastic polyurethane foam composition may also have a flexural strength within 5% of the flexural strength of a reference thermoplastic polyurethane foam that does not contain biomass-based carbonaceous particulate matter, as measured according to ASTM-C203. The flexural strength of the thermoplastic polyurethane foam composition may be from 5 pounds per square inch to 80 pounds per square inch, from 5 pounds per square inch to 60 pounds per square inch, from 6 pounds per square inch to 50 pounds per square inch, from 7 pounds per square inch to 40 pounds per square inch, from 8 pounds per square inch to 30 pounds per square inch, from 9 pounds per square inch to 25 pounds per square inch, and from 10 pounds per square inch to 20 pounds per square inch.

[0074] As another non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the thermoplastic polyurethane foam composition can have a compression strength at 50% strain of at least 40 kilopascals as measured according to ASTM-D3575-D. The thermoplastic polyurethane foam composition can also have a compression strength at 50% strain of at least 60 kilopascals as measured according to ASTM-D3575-D, at least 80 kilopascals as measured according to ASTM-D3575-D, at least 100 kilopascals as measured according to ASTM-D3575-D, at least 150 kilopascals as measured according to ASTM-D3575-D, at least 200 kilopascals as measured according to ASTM-D3575-D, or at least 250 kilopascals as measured according to ASTM-D3575-D. The thermoplastic polyurethane foam composition can even have a compression strength at 50% strain of at least 300 kilopascals as measured according to ASTM-D3575-D. The thermoplastic polyurethane foam composition has a compression strength at 50% strain of 40 kilopascals to 1500 kilopascals, 40 kilopascals to 1000 kilopascals, 40 kilopascals to 800 kilopascals, 40 kilopascals to 600 kilopascals, 40 kilopascals to 500 kilopascals, 60 kilopascals to 1500 kilopascals, 100 kilopascals to 1500 kilopascals, 150 kilopascals to 1000 kilopascals, 200 kilopascals to 600 kilopascals, 250 kilopascals to 400 kilopascals, 300 kilopascals to 350 kilopascals, about 300 kilopascals, about 325 kilopascals, or about 350 kilopascals.

[0075] As another non-limiting example of the mechanical properties of the thermoplastic polyurethane foam composition, the thermoplastic polyurethane foam composition has a compressive strength at 75% strain of 80 kilopascals to 13,500 kilopascals, 80 kilopascals to 3,000 kilopascals, 150 kilopascals to 3,000 kilopascals, 200 kilopascals to 3,000 kilopascals, 300 kilopascals to 3,000 kilopascals, 400 kilopascals to 3,000 kilopascals, 500 kilopascals to 3,000 kilopascals, 310 kilopascals to 10,000 kilopascals, 310 kilopascals to 5,000 kilopascals, 310 kilopascals to 3,000 kilopascals, 310 kilopascals to 2,000 kilopascals, 310 kilopascals to 1,000 kilopascals, 400 kilopascals to 800 kilopascals, 600 kilopascals to 800 kilopascals, 650 kilopascals to 750 kilopascals, about 700 kilopascals, about 800 kilopascals, about 900 kilopascals, or about 1,000 kilopascals.

[0076] 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, for example, additional colorants, stabilizers, such as ultraviolet 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. Further, the thermoplastic polyurethane foam composition may include a resin useful for improving the foaming of the thermoplastic polyurethane foam composition and / or a coupling agent for better mixing and dispersion.

[0077] A thermoplastic foam composition comprising a thermoplastic polyurethane foam composition may be formed into beads or into a final product (e.g., a low-density, high-rigidity article). It should be understood that the final product may be a component of a larger assembly. The final product may be for automotive applications. In non-limiting examples of automotive applications, the final product may be a seat substrate, seat cushion, headrest, bumper core, armrest, trunk or cargo space component, door panel component, headliner component, spacer, load floor, or battery case. It should also be understood that the final product need not be for automotive applications. In non-limiting examples of non-automotive applications, the final product may be a shoe component such as a shoe midsole or insole, a packaging tray, a protective packaging box, industrial dunnage, and industrial packaging. In embodiments where the thermoplastic foam composition comprises foamed polypropylene, the article may in particular be 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 shoe midsoles or insoles.

[0078] It should be understood that the unactivated biomass-based carbonaceous particulate material affects the foamability, fusibility, and performance of the beads. The unactivated biomass-based carbonaceous particulate material also affects processability, cell morphology, thermal properties, and the final performance of the beads when formed into a final product thereafter. The thermoplastic foam composition may also include two distinct crystal melting points. That is, the thermoplastic foam composition may have a low crystal melting point and a high crystal melting point. The low crystal melting point and the high crystal melting point improve the processability of the thermoplastic foam composition as described below. Furthermore, it has been found that the unactivated biomass-based carbonaceous particulate material may lower either the low crystal melting point of the thermoplastic foam composition, the high crystal melting point of the thermoplastic foam composition, or both the low crystal melting point and the high crystal melting point of the thermoplastic foam composition. As a non-limiting example, the low crystal melting point may be from 110 °C to 150 °C, and the high crystal melting point may be from 150 °C to 170 °C.

[0079] A method for producing a thermoplastic foam composition is also provided. The method may include the step of extruding a thermoplastic material and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic material. The thermoplastic material may be extruded directly as a thermoplastic foam. Alternatively, the method may include the step of foaming the thermoplastic material to form a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam.

[0080] The step of extruding the thermoplastic material can be achieved using an extruder including, but not limited to, a single-screw extruder or a twin-screw extruder. Although not essential, the length-to-diameter ratio of the extruder may be about 36:1, and the extruder may have a coarse screw configuration. By the step of extruding the thermoplastic material, the thermoplastic material and the unactivated biomass-based carbonaceous particulate material are melt-blended. The step of extruding the thermoplastic material may further include extruding unactivated biomass-based carbonaceous particulate materials of various different particle sizes, optionally in a plurality of different resins, and optionally with one or more additives. The relative weight percentage of the unactivated biomass-based carbonaceous particulate material in the thermoplastic foam composition does not significantly affect the rheological properties of the thermoplastic foam composition such as viscosity, so it does not significantly affect the melt pressure or the extruder torque, and does not increase the energy consumption of the extruder during the step of extruding the thermoplastic material. Therefore, the unactivated biomass-based carbonaceous particulate material does not adversely affect the 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 pelletizing the extruded thermoplastic material into pellets using a pelletizer. The pelletizing of the extruded thermoplastic material into pellets using a pelletizer can be achieved before the pellets come into contact with the water bath. It should also be understood that a thin film of about 40 microns can be formed by the extrusion process.

[0081] The step of foaming a thermoplastic material to form a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated therein may be achieved using an autoclave and may further include the use of a blowing agent. The autoclave may be set at a temperature of about 80°C to about 250°C, about 80°C to about 200°C, about 100°C to about 180°C, about 120°C to about 150°C, about 125°C to about 140°C, about 125°C to about 135°C, about 125°C, about 130°C, or about 135°C. The thermoplastic material may be placed in the autoclave for 1 minute to 2 hours, 20 minutes to 1 hour, or about 1 hour. The step of foaming the thermoplastic material to form a thermoplastic foam composition can also be achieved under pressure. More specifically, the thermoplastic material may be under a pressure of 200 pounds per square inch to 1200 pounds per square inch, 500 pounds per square inch to 1100 pounds per square inch, 600 pounds per square inch to 1000 pounds per square inch, 700 pounds per square inch to 900 pounds per square inch, or about 800 pounds per square inch, etc., but is not limited thereto. The specific temperature and pressure associated with the step of foaming the thermoplastic material can be determined according to the specific thermoplastic material to avoid the risk of rupture of the thermoplastic material.

[0082] The step of foaming 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 foaming the thermoplastic material may further include reducing the pressure of the thermoplastic material, as a result of which the thermoplastic material foams due to the thermodynamic instability caused by the rapid pressure drop to form a thermoplastic foam composition. Although not essential, the step of foaming the thermoplastic material may be achieved by two or more separate foaming processes, and with each subsequent foaming, the density of the thermoplastic foam composition is further reduced. The step of foaming the thermoplastic material may further include washing the thermoplastic foam composition with water, optionally deionized water, and removing the suspension stabilizer if present.

[0083] The unactivated biomass-based carbonaceous particulate material can act as a cell nucleation site such as a cell non-uniform nucleation site or as a nucleating agent for crystallization during the step of foaming a thermoplastic material to form a thermoplastic foam composition. Thus, additional additives may not be required to function as a nucleation site or a nucleating agent. Further, the unactivated biomass-based carbonaceous particulate material acts to limit the size of the cells defined by the thermoplastic foam composition and thus can also increase the cell uniformity. It should be understood that the unactivated biomass-based carbonaceous particulate material is solid and does not have to act to increase the cell size during the step of foaming a thermoplastic material to form a thermoplastic foam composition. Therefore, it should be understood that it is a significant improvement that a thermoplastic foam composition comprising a thermoplastic foam and an unactivated biomass-based carbonaceous particulate material encapsulated therein also has high elongation at break, a controlled crystallization rate, and good rheological properties. As described above, the thermoplastic foam composition may contain additives other than the unactivated biomass-based carbonaceous particulate material. In another non-limiting example, the thermoplastic foam composition may contain other cell nucleating agents, which may be referred to as other nucleation sites and / or co-nucleating agents, for crystallization during the step of foaming a thermoplastic material to form a thermoplastic foam composition.

[0084] The step of foaming the thermoplastic material may be further defined as a step of foaming the pellets to form foamed beads. Thus, the step of foaming 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, through pressurization of the pellets as described herein. The step of foaming the pellets may further include depressurizing the pellets such that the pellets foam to form foamed beads that include a thermoplastic foam and unactivated biomass-based carbonaceous particulate material encapsulated within the thermoplastic foam. The pellets foam to form foamed beads due to the thermodynamic instability caused by a rapid pressure drop. The step of foaming the pellets may further include washing the foamed beads with water, optionally deionized water, to remove the suspension stabilizer if present.

[0085] The method may further include a step of forming a final product using a thermoplastic foam composition that includes a thermoplastic foam and unactivated biomass-based carbonaceous particulate material encapsulated by the thermoplastic foam. The step of forming the final product can be achieved using a press, such as but not limited to a steam chest press, a hydraulic press, or a resin press, to form the final product. Additionally or alternatively, the step of forming the final product may be achieved by bonding using a binder such as an adhesive. The press may induce sintering of the thermoplastic foam composition. More specifically, in embodiments where foamed beads are formed, the foamed beads may be sintered. It should be understood that the carbon footprint of the method can be further reduced by utilizing low steam pressure in the press. Also, depending on the specific formulation and specific processing parameters of the thermoplastic foam composition, the low crystalline melting point of the thermoplastic foam composition is reduced compared to a similar composition containing carbon black instead of the unactivated biomass-based carbonaceous particulate material, and thus it should also be understood that the carbon footprint of the method can be further reduced.

[0086] As described herein, the thermoplastic foam composition may include a low crystalline melting point and a high crystalline melting point, which can be collectively referred to as a double melting curve. More specifically, the foam beads may have a low crystalline melting point and a high crystalline melting point. By the process of forming a final product using the thermoplastic foam composition, significant benefits are obtained 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 process of forming the final product, the temperature of the press is preferably between the low crystalline melting point and the high crystalline melting point, or the temperature of the press is preferably lower than the high crystalline melting point to ensure the structural integrity of the final product. Thus, during the process of forming the final product, the crystals having a low crystalline melting point melt and thus contribute to the sintering of the thermoplastic foam composition, while the crystals having a high crystalline melting point do not melt and thus contribute to maintaining the overall shape of the final product. As a non-limiting example, a thermoplastic foam composition comprising a foamed ethylene propylene 1-butylene terpolymer and 10 weight percent of unactivated biomass-based carbonaceous particulate material encapsulated within the foamed ethylene propylene 1-butylene terpolymer has a low crystalline melting point and a high crystalline melting point (i.e., a double dissolution curve), and thus, the final product formed from the thermoplastic foam composition exhibits no sintering problems or dimensional stability problems.

[0087] While not intending to be bound by theory, it is believed that encapsulating unactivated biomass-based carbonaceous particulate material within the thermoplastic foam of the thermoplastic foam composition improves the dimensional stability of the thermoplastic foam composition. Typically, after forming the final product, the final product must be placed in a hot room or container (e.g., a "hot room") at a temperature, for example, of about 80 °C or less for about 4 to 8 hours in order to reduce the possibility of dimensional changes in the article. During this period at high temperature, a typical final product stabilizes and the pressure within the individual cells equilibrates such that the dimensions of a typical final product do not change significantly, even if they do change compared to immediately after formation. If a typical final product is not placed in a hot room or container at high temperature for a certain period of time, the dimensions of the final product will change and the final product may fall outside the acceptable range.

[0088] However, by encapsulating unactivated biomass-based carbonaceous particulate matter in a thermoplastic foam, the dimensional stability of the thermoplastic foam composition is increased to such an extent that it is not necessary to place the final product formed from the thermoplastic foam composition in a high-temperature room or container. Without being bound by theory, it is believed that the unactivated biomass-based carbonaceous particulate matter 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 within each cell of the thermoplastic foam composition more uniform, and thus retains the dimensions of the final product. Retaining the dimensions of the final product is important to ensure that the final product is within the correct tolerances of the final product.

[0089] A method for producing a thermoplastic polyurethane foam composition is also provided. The method may include the step of extrusion molding a thermoplastic polyurethane material and a biomass-based carbonaceous particulate matter encapsulated in the thermoplastic polyurethane material. The thermoplastic polyurethane material may be directly extrusion molded as a thermoplastic polyurethane foam. Alternatively, the method may include the step of foaming the thermoplastic polyurethane material to form a thermoplastic polyurethane foam and a biomass-based carbonaceous particulate matter encapsulated in the thermoplastic polyurethane foam.

[0090] The following examples are intended to illustrate the present disclosure and should not be construed as limiting the scope of the present disclosure.

[0091] Examples 1-5 Examples 1 to 5 are of the thermoplastic foam composition according to the present disclosure and can be found in Tables 1 to 3. Each of Examples 1 to 5 corresponds to Tests 1 to 5 in Tables 1 to 3, respectively. The thermoplastic foam compositions used in Tests 1 to 5 of Tables 1 to 3 have the same composition, namely, a thermoplastic foam composition containing foamed polypropylene and 5 wt% of unactivated biomass-based carbonaceous particulate matter, but were produced under different processing parameters. Controls 1 and 2 in Tables 1 to 3 are not formed according to the present disclosure and are included to emphasize the advantages of the thermoplastic foam compositions described herein. More specifically, Controls 1 and 2 include typical foam compositions containing foamed polypropylene and 3 weight percent of carbon black.

[0092] Referring now to Table 1, the thermoplastic foam compositions of Tests 1 to 5 were formed such that the core density measured according to ASTM-D3575-W Test Method A was in the range of 17.9 grams / liter to 56.4 grams / liter. As can be seen in Table 1, for each of Tests 1 to 5, the modulus of elasticity measured according to ASTM-C203 Method I, Equation 13, was in the range of 406.4 pounds per square inch to 2009.3 pounds per square inch. Comparing Tests 1 to 5 in Table 1 with Controls 1 and 2, it is clear that the encapsulation of unactivated biomass-based carbonaceous particulate matter increases the modulus of elasticity of the thermoplastic foam composition. More specifically, comparing Test 4 here with Control 1, the nominal density and the core density are almost the same, but Test 4 has a much higher modulus of elasticity. The modulus of elasticity of Test 4 is 801.8, while the modulus of elasticity of Control 1 is only 670.1. Thus, it is clear that the modulus of elasticity of Test 4 is approximately 20% higher than that of a reference thermoplastic foam (e.g., Control 1) that does not contain unactivated biomass-based carbonaceous particulate matter.

[0093] Referring further to Table 1, in each of Tests 1 to 5, the compression set rate at both 25% strain and 50% strain was also measured in accordance with ASTM-3575-B. The compression set rate at 25% strain for Tests 1 to 5 was in the range of 4 to 16%, and the compression set rate at 50% strain for Tests 1 to 5 was in the range of 22 to 27%. In Table 1, when comparing Tests 1 to 5 with Controls 1 and 2, it is clear that the compression set rate at both 25% strain and 50% strain does not decrease much, if at all, even when encapsulating the unactivated biomass-based carbonaceous particulate matter. More specifically, when comparing Test 4 with Control 1 here, similar nominal density, similar core density, similar compression set rate at 25% strain, and similar compression set rate at 50% strain are seen. Therefore, in Test 4, it is clear that the compression set rate at 25% strain is within 25% of that of a reference thermoplastic foam (e.g., Control 1) that does not contain unactivated biomass-based carbonaceous particulate matter. Also, in Test 4, it is clear that the compression set rate at 50% strain is within 25% of that of a reference thermoplastic foam (e.g., Control 1) that does not contain unactivated biomass-based carbonaceous particulate matter.

[0094] Referring here to Table 2, in each of Tests 1 to 5, the flexural strength was further measured in accordance with ASTM-C203. The flexural strength of Tests 1 to 5 was in the range of 10.4 pounds per square inch to 53.1 pounds per square inch. In Table 2, when comparing Tests 1 to 5 with Controls 1 and 2, it is clear that the flexural strength does not decrease much, if at all, even when encapsulating the unactivated biomass-based carbonaceous particulate matter. More specifically, when comparing Test 4 with Control 1 here, similar nominal density, similar core density, and similar flexural strength are seen. Therefore, in Test 4, it is clear that the flexural strength is within 10% of that of a reference thermoplastic foam (e.g., Control 1) that does not contain unactivated biomass-based carbonaceous particulate matter. A similar conclusion is also derived from the comparison of the compressive strength at 10% strain, 25% strain, 50% strain, and 75% strain.

[0095] Referring to Table 3 here, in each of Tests 1 to 5, the tensile strength and elongation were further measured according to ASTM-3575-T. Considering Table 3, similar conclusions can be drawn regarding the effects of encapsulating the unactivated biomass-based carbonaceous particulate matter on the tensile strength and elongation. Therefore, it is clear that encapsulating the unactivated biomass-based carbonaceous particulate matter does not adversely affect the physical properties of the thermoplastic foam composition.

[0096] Furthermore, referring to Table 3, the measured horizontal burning rate of flammability according to Test Method FMVSS No. 302 indicated that the flame retardancy of the thermoplastic foam composition was significantly improved by encapsulating the unactivated biomass-based carbonaceous particulate matter. More specifically, in Tests 1 to 4, self-extinguishing properties were shown. In Test 5, the horizontal burning rate of flammability was less than 40 millimeters per minute. Comparing with Control 1 where the horizontal burning rate of flammability was 74 millimeters per minute, and also comparing with Control 2 where the horizontal burning rate of flammability was 47 millimeters per minute, it is clear that all of Tests 1 to 5 showed a significant improvement in flame retardancy. Such results were unexpected because the underlying unactivated biomass-based carbonaceous particulate matter and the derived biomass (e.g., wood) are flammable. Furthermore, flame retardancy is particularly important in end products for automotive applications such as sheet structures.

Table 1

Table 2

Table 3

[0097] Although the present invention has been described in an illustrative manner, it should be understood that the terms used are not limiting but are words for explanation. In light of the above teachings, many modifications and variations of the present invention are possible, 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, comprising: a thermoplastic foam; and an unactivated biomass-based carbonaceous particulate material encapsulated in the thermoplastic foam , wherein it has a core density of 12 g / l to 400 g / l as measured according to ASTM-D3575-W test method A, and it has a modulus of elasticity of 60 psi to 3500 psi as measured according to ASTM-C203 method I, equation 13, a thermoplastic foam composition.

2. The thermoplastic foam composition according to claim 1, wherein the unactivated biomass-based carbonaceous particulate material has a specific surface area of 150 m² / g to 495 m² / g of the unactivated biomass-based carbonaceous particulate material per gram.

3. The thermoplastic foam composition according to claim 1 or 2, wherein the unactivated biomass-based carbonaceous particulate material has a specific surface area of 190 m² / g to 495 m² / g of the unactivated biomass-based carbonaceous particulate material per gram.

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

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

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

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

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

9. The thermoplastic foam composition according to any one of claims 1 to 8, wherein the unactivated biomass-based carbonaceous particulate material has a proportion of modern carbon (pMC) of more 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 a foamed thermoplastic foam formed via a foaming agent.

11. The thermoplastic foam composition according to any one of claims 1 to 10, which is self-extinguishing and does not contain a flame retardant other than the unactivated biomass-based carbonaceous particulate material.

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

13. The thermoplastic foam composition according to claim 12, wherein the cells have an average size of less than 200 microns.

14. The thermoplastic foam composition according to any one of claims 1 to 13, wherein the thermoplastic foam substantially does not contain a cell nucleating agent other than the unactivated biomass-based carbonaceous particulate material.

15. The elastic modulus is measured according to ASTM-C203 method I, equation 13, and is at least 10% greater than the elastic modulus of a reference thermoplastic foam having the thermoplastic foam of the thermoplastic foam composition but not containing the unactivated biomass-based carbonaceous particulate material. The thermoplastic foam composition according to any one of claims 1 to 14.

16. The thermoplastic foam composition according to claim 15, wherein the compression set rate at 25% strain, measured according to ASTM-D3575-B, is within 25% of that of the reference thermoplastic foam not containing the unactivated biomass-based carbonaceous particulate material.

17. The thermoplastic foam composition according to any one of claims 15 or 16, having a flexural strength within 10% of the flexural strength of the reference thermoplastic foam not containing the unactivated biomass-based carbonaceous particulate material as measured according to ASTM-C203.

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

19. The thermoplastic foam-containing foamed polypropylene, the thermoplastic foam composition according to any one of claims 1 to 18.

20. The foamed polypropylene-containing at least 50 wt% of the copolymer of polypropylene, and 5 wt% to 30 wt% of ethylene-propylene rubber, the thermoplastic foam composition according to claim 19.

21. The foamed polypropylene-containing foamed ethylene-propylene 1-butylene terpolymer, the thermoplastic foam composition according to claim 19.

22. The foamed polypropylene having a core density of 12 grams / liter to 68 grams / liter as measured according to ASTM-D3575-W test method A, the thermoplastic foam composition according to any one of claims 19 to 21.

23. The core density is 12 grams / liter to 68 grams / liter as measured according to ASTM-D3575-W test method A, the thermoplastic foam composition according to any one of claims 1 to 21.

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

25. The thermoplastic foam-containing thermoplastic polyurethane, the thermoplastic foam composition according to any one of claims 1 to 18.

26. A thermoplastic polyurethane foam composition for low density and high rigidity articles, A thermoplastic polyurethane foam; and The biomass-based carbonaceous particulate matter encapsulated in the thermoplastic polyurethane foam Including, Having a core density of 80 grams / liter to 400 grams / liter as measured according to ASTM-D3575-W test method A, and Having an elastic modulus of 60 pounds / square inch to 700 pounds / square inch as measured according to ASTM-C203 method I, formula 13, a thermoplastic polyurethane foam composition.

27. The biomass-based carbonaceous particulate matter having a specific surface area of 150 square meters per gram of the biomass-based carbonaceous particulate matter to 2000 square meters per gram of the biomass-based carbonaceous particulate matter, the thermoplastic polyurethane foam composition according to claim 26.

28. The biomass-based carbonaceous particulate matter is further defined as unactivated biomass-based carbonaceous particulate matter, and the unactivated biomass-based carbonaceous particulate matter has a specific surface area of 150 square meters per gram to 495 square meters per gram of the unactivated biomass-based carbonaceous particulate matter. The thermoplastic polyurethane foam composition according to claim 27.

29. The biomass-based carbonaceous particulate matter is further defined as activated biomass-based carbonaceous particulate matter, and the activated biomass-based carbonaceous particulate matter has a specific surface area of 495 square meters per gram to 2000 square meters per gram of the activated biomass-based carbonaceous particulate matter. The thermoplastic polyurethane foam composition according to claim 27.

30. The biomass-based carbonaceous particulate matter is 0.1% by weight to 25% by weight of the thermoplastic polyurethane foam composition. The thermoplastic polyurethane foam composition according to any one of claims 26 to 29.

31. The biomass-based carbonaceous particulate matter is 0.5% by weight to 20% by weight of the thermoplastic polyurethane foam composition. The thermoplastic polyurethane foam composition according to any one of claims 26 to 30.

32. The biomass-based carbonaceous particulate matter is uniformly distributed and dispersed throughout the thermoplastic polyurethane foam. The thermoplastic polyurethane foam composition according to any one of claims 26 to 31.

33. The biomass-based carbonaceous particulate matter has a D50 particle size of 0.1 micron to 200 microns. The thermoplastic polyurethane foam composition according to any one of claims 26 to 32.

34. The biomass-based carbonaceous particulate matter has a D50 particle size of 1 micron to 50 microns. The thermoplastic polyurethane foam composition according to any one of claims 26 to 33.

35. The biomass-based carbonaceous particulate matter has a proportion of modern carbon (pMC) of more than 75% as measured according to ASTM D6866. The thermoplastic polyurethane foam composition according to any one of claims 26 to 34.

36. The thermoplastic polyurethane foam composition according to any one of claims 26 to 35, further defined as a foamed thermoplastic polyurethane foam formed via a foaming agent.

37. The thermoplastic polyurethane foam composition according to any one of claims 26 to 36, which is self-extinguishing and does not contain a flame retardant other than the biomass-based carbonaceous particulate material.

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

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

40. The thermoplastic polyurethane foam composition according to any one of claims 26 to 39, wherein the thermoplastic polyurethane foam substantially does not contain a cell nucleating agent other than the biomass-based carbonaceous particulate material.

41. The elastic modulus is measured according to ASTM-C203 Method I, Equation 13, and is at least 10% greater than the elastic modulus of a reference thermoplastic polyurethane foam having the thermoplastic polyurethane foam of the thermoplastic polyurethane foam composition but not containing the biomass-based carbonaceous particulate material. The thermoplastic polyurethane foam composition according to any one of claims 26 to 40.

42. The compression set rate at 25% strain, measured according to ASTM-D3575-B, is within 25% of that of the reference thermoplastic polyurethane foam not containing the biomass-based carbonaceous particulate material. The thermoplastic polyurethane foam composition according to claim 41.

43. The thermoplastic polyurethane foam composition according to any one of claims 41 or 42, having a flexural strength within 10% of the flexural strength of the reference thermoplastic polyurethane foam not containing the biomass-based carbonaceous particulate material, measured according to ASTM-C203.

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

45. The thermoplastic polyurethane foam composition according to any one of claims 26 to 44, having a core density of 100 g / l to 300 g / l as measured according to ASTM-D3575-W test method A.

46. The thermoplastic polyurethane foam composition according to any one of claims 26 to 45, having a core density of 150 g / l to 250 g / l as measured according to ASTM-D3575-W test method A.

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