Lignin-containing polyurethane materials and methods of making same

Abstract

The invention relates to a lignin-containing polyurethane material and a method for the production thereof. The invention relates to a polyurethane material which comprises polyol, lignin and a catalyst, and a reaction product of a polyisocyanate. The polyol comprises an amphiphilic polyoxyalkylene copolymer having at least two terminal primary or secondary hydroxyl groups. The amphiphilic polyoxyalkylene copolymer comprises a hydrophilic oxyalkylene group covalently bonded to a hydrophobic oxyalkylene group. The polyurethane material may be a polyurethane foam, and the lignin may comprise greater than 30% by weight of the polyurethane foam.

Description

Technical Field

[0001] The present disclosure relates to polyurethane materials comprising a high lignin loading and methods of making such polyurethane materials. Background Art

[0002] The information provided in this section is for a general introduction to the background of the present disclosure. The work of the currently named inventors described in this section, as well as aspects of the specification that may not have been otherwise determined to be prior art at the time of filing, are not expressly or implicitly admitted to be prior art to the present disclosure.

[0003] Lignin is a natural polyol and is a promising candidate for use as a polyol in the manufacture of polyurethane materials because it is abundant in nature and is a by-product of various manufacturing processes. Summary of the Invention

[0004] According to one or more embodiments of the present disclosure, a polyurethane material comprises the reaction product of a polyol, lignin, a catalyst; and a polyisocyanate. The polyol comprises an amphiphilic polyoxyalkylene copolymer having at least two terminal primary or secondary hydroxyl groups. The amphiphilic polyoxyalkylene copolymer comprises hydrophilic oxyalkylene groups covalently bonded to hydrophobic oxyalkylene groups.

[0005] The lignin can be a particulate material having an average particle size greater than or equal to 5 microns and less than or equal to 250 microns.

[0006] The lignin can account for more than 30% by weight of the polyurethane material. The lignin can be uniformly distributed throughout the polyurethane material.

[0007] The lignin can be a natural plant product, kraft lignin, soda lignin, organosolv lignin, sulfite lignin, lignocellulosic biomass, or a combination thereof. The lignin can be untreated with propoxylation, chemical grafting, heat treatment, hydrolysis, microwave radiation, or a combination thereof.

[0008] The amphiphilic polyoxyalkylene copolymer can comprise a copolymer of ethylene oxide and propylene oxide.

[0009] In an embodiment, the polyol can comprise a first amphiphilic polyoxyalkylene copolymer having a functionality greater than or equal to 2 and less than or equal to 10, a nominal molecular weight greater than or equal to 100 daltons and less than or equal to 10,000 daltons, and a hydroxyl value greater than or equal to 10 mg KOH / g and less than or equal to 400 mg KOH / g.

[0010] In an embodiment, the polyol may comprise a first amphiphilic polyoxyalkylene copolymer and a second amphiphilic polyoxyalkylene copolymer. The first amphiphilic polyoxyalkylene copolymer may have a functionality greater than or equal to 2 and less than or equal to 3, a nominal molecular weight greater than or equal to 6000 daltons and less than or equal to 7000 daltons, and a hydroxyl value greater than or equal to 20 mg KOH / g and less than or equal to 30 mg KOH / g. The second amphiphilic polyoxyalkylene copolymer may have a functionality greater than or equal to 4 and less than or equal to 6, a nominal molecular weight greater than or equal to 180 daltons and less than or equal to 1000 daltons, and a hydroxyl value greater than or equal to 200 mg KOH / g and less than or equal to 400 mg KOH / g.

[0011] In an embodiment, the polyol may comprise a polyoxyalkylene copolymer having the formula R–[(OA 1 ) a (OA 2 ) b (OA 3 ) c –OH] x , where R is a cyclic or acyclic aliphatic hydrocarbon group; AO 1 and AO 3 are oxyethylene; AO 2 is oxypropylene; a, b, and c are integers; a + b + c is greater than or equal to 3 and less than or equal to 300; and x is an integer greater than or equal to 2 and less than or equal to 6.

[0012] In this case, in some embodiments, the polyoxyalkylene copolymer may be a block copolymer, and a, b, and c may each be an integer greater than or equal to 2.

[0013] The polyisocyanate may include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0014] The catalyst may include a metal-containing catalyst and a tertiary amine catalyst.

[0015] The polyurethane material may further comprise a surfactant, the surfactant including a silicone-containing material.

[0016] The polyurethane material may further comprise a crosslinking agent, the crosslinking agent comprising a polyol having a molecular weight greater than or equal to 50 g / mol and less than or equal to 300 g / mol.

[0017] The polyurethane material may further comprise additives, which include flame retardants, viscosity regulators, antimicrobial agents, pigments, fragrances, antioxidants, UV light stabilizers, or combinations thereof.

[0018] The polyurethane material may further comprise a blowing agent.

[0019] The polyurethane material may be a polyurethane foam having a density greater than or equal to 40 kg / m³ and less than or equal to 400 kg / m³ and a compression force deflection greater than or equal to 4 kPa and less than or equal to 800 kPa.

[0020] According to one or more embodiments of the present disclosure, a polyurethane foam comprises the reaction product of a polyol, lignin, a surfactant, a catalyst, and a polyisocyanate. The polyol comprises a copolymer of oxyethylene and oxypropylene. The copolymer has at least two terminal primary or secondary hydroxyl groups. The lignin is uniformly distributed throughout the polyurethane foam and accounts for greater than or equal to 30% by weight of the polyurethane foam. The polyurethane foam has a density greater than or equal to 40 kg / m³ and less than or equal to 400 kg / m³ and a compression force deflection greater than or equal to 4 kPa and less than or equal to 800 kPa.

[0021] The lignin may be a natural plant product, kraft lignin, soda lignin, organosolv lignin, sulfite lignin, lignocellulosic biomass, or combinations thereof. The lignin may not be subjected to propoxylation, chemical grafting, heat treatment, hydrolysis, microwave radiation, or combinations thereof. The lignin may be a granular material having an average particle size greater than or equal to 5 µm and less than or equal to 250 µm.

[0022] The copolymer has a functionality greater than or equal to 2 and less than or equal to 6, a nominal molecular weight greater than or equal to 100 Dalton and less than 10000 Dalton, and a hydroxyl value greater than or equal to 10 mg KOH / g and less than or equal to 400 mg KOH / g.

[0023] According to one or more embodiments of the present disclosure, a method of manufacturing a polyurethane material includes mixing a polyol and lignin together at a speed greater than or equal to 200 revolutions per minute and less than or equal to 10000 revolutions per minute for a duration less than or equal to 1 hour to form a polyol mixture. The mass ratio of lignin to polyol (lignin: polyol) in the polyol mixture is greater than 3:7 and less than or equal to 9:1. A catalyst is introduced into the polyol mixture to form an intermediate mixture. A polyisocyanate is introduced into the intermediate mixture to form a polyurethane material.

[0024] The present invention discloses the following solutions:

[0025] Solution 1. A polyurethane material, which comprises the reaction product of the following substances:

[0026] A polyol, which comprises an amphiphilic polyoxyalkylene copolymer having at least two terminal primary or secondary hydroxyl groups, and the amphiphilic polyoxyalkylene copolymer comprises a hydrophilic oxyalkylene group covalently bonded to a hydrophobic oxyalkylene group;

[0027] Lignin;

[0028] A catalyst; and

[0029] A polyisocyanate.

[0030] Solution 2. The polyurethane material according to Solution 1, wherein the lignin is a granular material with an average particle size greater than or equal to 5 microns and less than or equal to 250 microns.

[0031] Solution 3. The polyurethane material according to Solution 1, wherein the lignin accounts for more than 30% by weight of the polyurethane material, and the lignin is uniformly distributed throughout the polyurethane material.

[0032] Solution 4. The polyurethane material according to Solution 1, wherein the lignin is a natural plant product, kraft lignin, soda lignin, organosolv lignin, sulfite lignin, lignocellulosic biomass or a combination thereof, and the lignin is not subjected to propoxylation, chemical grafting, heat treatment, hydrolysis, microwave radiation or a combination thereof.

[0033] Solution 5. The polyurethane material according to Solution 1, wherein the amphiphilic polyoxyalkylene copolymer comprises a copolymer of ethylene oxide and propylene oxide.

[0034] Solution 6. The polyurethane material according to Solution 1, wherein the polyol comprises a first amphiphilic polyoxyalkylene copolymer having a functionality greater than or equal to 2 and less than or equal to 10, a nominal molecular weight greater than or equal to 100 daltons and less than or equal to 10,000 daltons, and a hydroxyl value greater than or equal to 10 mg potassium hydroxide / g and less than or equal to 400 mg potassium hydroxide / g.

[0035] Embodiment 7. The polyurethane material according to Embodiment 6, wherein the first amphiphilic polyalkylene oxide copolymer has a functionality greater than or equal to 2 and less than or equal to 3, a nominal molecular weight greater than or equal to 6000 daltons and less than or equal to 7000 daltons, and a hydroxyl value greater than or equal to 20 mg KOH / g and less than or equal to 30 mg KOH / g, and wherein the polyol further comprises a second amphiphilic polyalkylene oxide copolymer having a functionality greater than or equal to 4 and less than or equal to 6, a nominal molecular weight greater than or equal to 180 daltons and less than or equal to 1000 daltons, and a hydroxyl value greater than or equal to 200 mg KOH / g and less than or equal to 400 mg KOH / g.

[0036] Embodiment 8. The polyurethane material according to Embodiment 1, wherein the polyol comprises a polyalkylene oxide copolymer having the formula R–[(OA 1 ) a (OA 2 ) b (OA 3 ) c –OH] x , wherein:

[0037] R is a cyclic or acyclic aliphatic hydrocarbon group;

[0038] AO 1 and AO 3 are oxyethylene;

[0039] AO 2 is oxypropylene;

[0040] a, b, and c are integers;

[0041] a + b + c is greater than or equal to 3 and less than or equal to 300; and

[0042] x is an integer greater than or equal to 2 and less than or equal to 6.

[0043] Embodiment 9. The polyurethane material according to Embodiment 8, wherein the polyalkylene oxide copolymer is a block copolymer, and wherein a, b, and c are each integers greater than or equal to 2.

[0044] Embodiment 10. The polyurethane material according to Embodiment 1, wherein the polyisocyanate includes toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0045] Embodiment 11. The polyurethane material according to Embodiment 1, wherein the catalyst includes a metal-containing catalyst and a tertiary amine catalyst.

[0046] Embodiment 12. The polyurethane material according to Embodiment 1 further comprises a surfactant, and the surfactant comprises a silicone-containing material.

[0047] Embodiment 13. The polyurethane material according to Embodiment 1 further comprises a crosslinking agent, and the crosslinking agent comprises a polyol having a molecular weight greater than or equal to 50 g / mol and less than or equal to 300 g / mol.

[0048] Embodiment 14. The polyurethane material according to Embodiment 1 further comprises an additive, and the additive comprises a flame retardant, a viscosity regulator, an antimicrobial agent, a pigment, a fragrance, an antioxidant, a UV light stabilizer, or a combination thereof.

[0049] Embodiment 15. The polyurethane material according to Embodiment 1 further comprises a blowing agent.

[0050] Embodiment 16. The polyurethane material according to Embodiment 1, wherein the polyurethane material is a polyurethane foam, and the polyurethane foam has a density greater than or equal to 40 kg / m³ and less than or equal to 400 kg / m³ and a compression force deflection greater than or equal to 4 kPa and less than or equal to 800 kPa.

[0051] Embodiment 17. A polyurethane foam comprising the reaction product of:

[0052] a polyol, the polyol comprising a copolymer of oxyethylene and oxypropylene, the copolymer having at least two terminal primary or secondary hydroxyl groups;

[0053] lignin, the lignin being uniformly distributed throughout the polyurethane foam and accounting for greater than or equal to 30% by weight of the polyurethane foam;

[0054] a surfactant;

[0055] a catalyst; and

[0056] a polyisocyanate,

[0057] wherein the polyurethane foam has a density greater than or equal to 40 kg / m³ and less than or equal to 400 kg / m³ and a compression force deflection greater than or equal to 4 kPa and less than or equal to 800 kPa.

[0058] Embodiment 18. The polyurethane foam according to Embodiment 17, wherein the lignin is a natural plant product, kraft lignin, soda lignin, organosolv lignin, sulfite lignin, lignocellulosic biomass, or a combination thereof, wherein the lignin is not subjected to propoxylation, chemical grafting, heat treatment, hydrolysis, microwave radiation, or a combination thereof, and wherein the lignin is a particulate material having an average particle size greater than or equal to 5 µm and less than or equal to 250 µm.

[0059] Embodiment 19. The polyurethane foam according to Embodiment 17, wherein the copolymer has a functionality greater than or equal to 2 and less than or equal to 6, a nominal molecular weight greater than or equal to 100 daltons and less than or equal to 10,000 daltons, and a hydroxyl value greater than or equal to 10 mg potassium hydroxide / gram and less than or equal to 400 mg potassium hydroxide / gram.

[0060] Embodiment 20. A method for manufacturing a polyurethane material, the method comprising:

[0061] Mixing a polyol and lignin together at a speed greater than or equal to 200 revolutions per minute and less than or equal to 10,000 revolutions per minute for a duration less than or equal to 1 hour to form a polyol mixture, wherein the mass ratio of the lignin to the polyol (lignin:polyol) in the polyol mixture is greater than 3:7 and less than or equal to 9:1;

[0062] Introducing a catalyst into the polyol mixture to form an intermediate mixture; and

[0063] Introducing a polyisocyanate into the intermediate mixture to form a polyurethane material.

[0064] Further applicable fields of the present disclosure will be apparent from the detailed description, claims, and drawings. The detailed description and specific embodiments are only intended to illustrate and are not intended to limit the scope of the present disclosure. Description of the Drawings

[0065] The present disclosure will be more fully understood from the detailed description and the accompanying drawings, wherein:

[0066] Figure 1 is a schematic diagram of a motor vehicle including a polyurethane material.

[0067] In the drawings, reference numerals may be reused to designate similar and / or identical elements. Detailed Description

[0068] The present disclosure relates to polyurethane materials containing unmodified lignin and methods for manufacturing such polyurethane materials. The polyurethane materials manufactured according to one or more embodiments of the present disclosure may be polyurethane foams (e.g., integral skin foam), polyurethane adhesives, polyurethane elastomers, polyurethane coatings, or polyurethane fibers. In embodiments where the polyurethane material includes a polyurethane foam, the polyurethane foam may be a soft foam, a semi-rigid foam, or a rigid foam. Now refer to Figure 1, in embodiments, the polyurethane material can be a component of a motor vehicle 10. Examples of motor vehicle components that can be formed of and / or include the polyurethane materials of the present disclosure include package trays, impact pads (e.g., automotive rear fascias, knee bolsters, and / or door panels), vehicle seats, headrests, armrests, consoles, headliners, steering wheels, instrument panels, dashboards, load floors, and cargo and storage compartments.

[0069] In embodiments where the polyurethane material is a polyurethane foam, the polyurethane foam can have a density greater than or equal to 40 kilograms per cubic meter (kg / m 3 ), optionally greater than or equal to 50 kg / m 3 , optionally greater than or equal to 100 kg / m 3 , optionally greater than or equal to 150 kg / m 3 , optionally greater than or equal to 170 kg / m 3 , optionally greater than or equal to 180 kg / m 3 , optionally greater than or equal to 200 kg / m 3 , or optionally greater than or equal to 215 kg / m 3 , and less than or equal to 400 kg / m 3 , optionally less than or equal to 300 kg / m 3 , or optionally less than or equal to 250 kg / m 3 . Additionally, in embodiments where the polyurethane material is a polyurethane foam, the polyurethane foam can have a compression force deflection, as measured by ASTM D1621 using a 25% deflection value at ambient temperature (e.g., a temperature of about 25 degrees Celsius (°C)), greater than or equal to 45 kilopascals (kPa), optionally greater than or equal to 100 kPa, optionally greater than or equal to 120 kPa, optionally greater than or equal to 130 kPa, optionally greater than or equal to 200 kPa, optionally less than or equal to 250 kPa, optionally greater than or equal to 300 kPa, optionally greater than or equal to 400 kPa, optionally greater than or equal to 500 kPa, or optionally greater than or equal to 600 kPa, and less than or equal to 1500 kPa, optionally less than or equal to 1000 kPa, or optionally less than or equal to 800 kPa.

[0070] According to one or more embodiments of the present disclosure, a polyurethane material comprises the reaction product of a polyol, lignin, polyisocyanate, catalyst, optional surfactant, optional crosslinker, optional blowing agent, and optional additives. The polyurethane material can be manufactured by forming a reaction mixture comprising a polyol, lignin, polyisocyanate, catalyst, optional surfactant, optional crosslinker, optional blowing agent, and optional additives. The polyol and lignin components can together constitute the isocyanate-reactive component or resin component of the reaction mixture. The amount of each individual component in the reaction mixture can be expressed relative to the amount of the resin component in the reaction mixture. For example, the amount of each component in the reaction mixture can be expressed in parts by weight per hundred units of resin (PHR).

[0071] The polyol is formulated to ensure that the lignin is uniformly and homogeneously dispersed in the reaction mixture used to form the polyurethane material, and thus effectively eliminates the need for vigorous mechanical mixing (e.g., ball milling) of the reaction mixture and / or the need for chemical, thermal, or other modification of the lignin prior to manufacturing the polyurethane material. The polyol used to manufacture the polyurethane materials of the present disclosure effectively allows for the production of polyurethane materials having a relatively high lignin loading (e.g., greater than 30 wt%) and a substantially uniform physical appearance and substantially uniform chemical composition. Because the polyol allows the lignin to be easily and uniformly dispersed throughout the polyurethane material during manufacturing without the need for aggressive mechanical mixing and without the need for prior chemical and / or heat treatment of the lignin, using less time and less energy compared to other manufacturing methods, the polyol can be used to efficiently and consistently manufacture polyurethane materials with high lignin loading and high reproducibility.

[0072] The polyol comprises at least one amphiphilic polyoxyalkylene copolymer having at least two terminal primary or secondary hydroxyl groups and comprising hydrophilic oxyalkylene groups (e.g., ethylene oxide groups) covalently bonded to hydrophobic oxyalkylene groups (e.g., propylene oxide groups). In an embodiment, the polyol can comprise at least one amphiphilic polyoxyalkylene copolymer having at least two terminal primary hydroxyl groups. The hydrophilic oxyalkylene groups and the hydrophobic oxyalkylene groups can be randomly distributed along the polymer chain of the polyol, or the hydrophilic oxyalkylene groups and the hydrophobic oxyalkylene groups can be arranged in defined blocks. A primary hydroxyl group (-OH) is directly bonded to a primary carbon atom that is directly bonded to a single carbon atom, and a secondary hydroxyl group is directly bonded to a secondary carbon atom that is directly bonded to two carbon atoms.

[0073] The polyol can comprise at least one polyoxyalkylene copolymer having the formula (1):

[0074] R–[(OA 1 ) a (OA 2 ) b (OA 3 )c –OH] x ,(1)

[0075] wherein R is a polyvalent aliphatic hydrocarbon, AO 1 , AO 2 and AO 3 are each independently an alkylene oxide group, a and b are integers, c is zero or an integer, a + b + c is greater than or equal to 3 and less than or equal to 300, and x is an integer greater than or equal to 2. In an embodiment, x can be greater than or equal to 3, optionally greater than or equal to 4, optionally greater than or equal to 6, or optionally greater than or equal to 8, and less than or equal to 10.

[0076] R can be a cyclic or acyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms and 2 or more bonding sites. For example, the number of bonding sites on the R group in the polyalkylene oxide copolymer of formula (1) can be greater than or equal to 2, optionally greater than or equal to 3, optionally greater than or equal to 4, optionally greater than or equal to 6, or optionally greater than or equal to 8, and less than or equal to 10. Examples of aliphatic hydrocarbon groups having 2 bonding sites include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, cyclopentylene, and cyclohexylene. In addition, examples of aliphatic hydrocarbon groups having 3 to 6 bonding sites include the residues obtained by removing hydroxyl groups from polyols such as trimethylolpropane, glycerol, pentaerythritol, sorbitol, 1,2,3-trihydroxycyclohexane, or 1,3,5-trihydroxycyclohexane.

[0077] The value of x in the polyalkylene oxide copolymer of formula (1) directly corresponds to the number of bonding sites on the R group. For example, when R has 2 bonding sites, the value of x is 2. In addition, the value of x corresponds to the number of isocyanate-reactive functional groups (i.e., hydroxyl groups) in the polyalkylene oxide copolymer of formula (1), which can be referred to as the “functionality” of the polyol and / or the polyalkylene oxide copolymer of formula (1). In an embodiment, the polyol can have a functionality greater than or equal to 2, optionally greater than or equal to 3, optionally greater than or equal to 4, optionally greater than or equal to 6, or optionally greater than or equal to 8, and less than or equal to 10.

[0078] In the polyalkylene oxide copolymer of formula (1), the alkylene oxide groups (AO 1 , AO 2 and AO 3 ) each independently have the formula -O-R 1 -, where R 1 is a straight-chain or branched divalent hydrocarbon group, and wherein AO 2 is different from AO 1 and AO 3. Examples of straight-chain or branched-chain divalent hydrocarbon groups include ethylene, propylene, butylene, pentylene, isopropylidene, hexylene, heptylene, octylene, nonylene, decylene, cyclopentylene, and cyclohexylene. Each oxyalkylene group (AO 1 , AO 2 , and AO 3 ) can be hydrophilic or hydrophobic. In an embodiment, at least one oxyalkylene group is a hydrophilic group (e.g., an ethylene oxide group), and at least one oxyalkylene group is a hydrophobic group (e.g., a propylene oxide group). In an embodiment, AO 1 is a hydrophilic oxyalkylene group, AO 2 is a hydrophobic oxyalkylene group, and when present, AO 3 is a hydrophilic oxyalkylene group. When c is an integer greater than or equal to 1 and AO 3 is a hydrophilic oxyalkylene group, the polyoxyalkylene copolymer of formula (1) can be referred to as having a hydrophilic capping. In an embodiment, the polyol can be a block copolymer. In this case, in the polyoxyalkylene copolymer of formula (1), a is an integer greater than or equal to 2, b is an integer greater than 2, and c (when present) is an integer greater than or less than 2.

[0079] The amphiphilic polyoxyalkylene copolymer can have a nominal molecular weight greater than or equal to 100 daltons, optionally greater than or equal to 500 daltons, optionally greater than or equal to 2000 daltons, optionally greater than or equal to 3000 daltons, optionally greater than or equal to 4000 daltons, optionally greater than or equal to 5000 daltons, or optionally greater than or equal to 6000 daltons, and less than or equal to 10000 daltons. The hydroxyl value of the polyol is defined as the number of milligrams (mg) of potassium hydroxide (KOH) required to neutralize the acetic acid absorbed when 1 gram (g) of the polyol is acetylated. The polyol can have a hydroxyl value greater than or equal to 10 mg KOH / g, optionally greater than or equal to 20 mg KOH / g, and less than or equal to 400 mg KOH / g, optionally less than or equal to 350 mg KOH / g, or optionally less than or equal to 30 mg KOH / g. The polyol can have a viscosity greater than or equal to 1000 centipoise (cP), optionally greater than or equal to 1200 cP, optionally greater than or equal to 1300 cP, and less than or equal to 2500 cP, or optionally less than or equal to 1500 cP at 77 degrees Fahrenheit (°F).

[0080] The polyol can be present in the reaction mixture for forming the polyurethane material in a mass ratio greater than or equal to 10 parts per hundred resin (phr), optionally greater than or equal to 20 phr, optionally greater than or equal to 30 phr, optionally greater than or equal to 40 phr, or optionally greater than or equal to 50 phr, and less than or equal to 70 phr.

[0081] In an embodiment, the polyol may include a first polyol and a second polyol. The first polyol and / or the second polyol may comprise at least one amphiphilic polyoxyalkylene copolymer comprising a hydrophilic oxyalkylene group covalently bonded to a hydrophobic oxyalkylene group. In an embodiment, the first polyol and / or the second polyol may comprise a copolymer of oxyethylene and oxypropylene. The functionality of the first polyol may be less than the functionality of the second polyol. For example, the first polyol may have a functionality of 3 and the second polyol may have a functionality of 4. Additionally, the hydroxyl value of the first polyol may be less than the hydroxyl value of the second polyol. For example, the first polyol may have a hydroxyl value greater than or equal to 20 mg KOH / g and less than or equal to 30 mg KOH / g, and the second polyol may have a hydroxyl value including greater than or equal to 200 mg KOH / g and less than or equal to 400 mg KOH / g. The nominal molecular weight of the first polyol may be greater than the nominal molecular weight of the second polyol. For example, the first polyol may have a nominal molecular weight greater than or equal to 6000 daltons and less than or equal to 7000 daltons (e.g., about 6500 daltons), and the second polyol may have a nominal molecular weight greater than or equal to 150 daltons and less than or equal to 1000 daltons (e.g., about 740 daltons). The viscosity of the first polyol may be less than the viscosity of the second polyol. For example, the first polyol may have a viscosity at 77°F greater than or equal to 1 centipoise (cP), or optionally greater than or equal to 1200 cP and less than or equal to 1500 cP (e.g., about 1370 cP), and the second polyol may have a viscosity at 77°F greater than or equal to 1600 cP and less than or equal to 2000 cP (e.g., about 1800 cP). In an embodiment where the polyol includes a first polyol and a second polyol, the first polyol and the second polyol may each independently be present in a reaction mixture for forming a polyurethane material in a mass ratio greater than or equal to 1 PHR, optionally greater than or equal to 5 PHR, optionally greater than or equal to 10 PHR, optionally greater than or equal to 20 PHR, optionally greater than or equal to 30 PHR, optionally greater than or equal to 40 PHR, or optionally greater than or equal to 50 PHR, and less than or equal to 69 PHR, or optionally less than or equal to 60 PHR.

[0082] The lignin is formulated to provide suitable rigidity to the polyurethane material while minimizing the amount of polyol required to achieve such rigidity in the reaction mixture. The lignin can be a natural product (e.g., natural hardwood, softwood, bamboo, and / or other natural plant products) and / or a by-product of one or more manufacturing processes, including biorefining processes useful for papermaking and various chemical pulping processes such as sulfate, soda, organic solvent, and / or sulfite. The lignin can be unmodified, meaning that the lignin can be produced without chemical modification, functionalization, and / or heat treatment after being produced as a natural product or a by-product of a manufacturing process (e.g., a biorefining process or a chemical pulping process). For example, the lignin can be untreated with propoxylation, chemical grafting (e.g., grafting with polyethylene glycol), heat treatment, hydrolysis, and / or microwave liquefaction. In embodiments, the lignin can comprise unmodified sulfate lignin, soda lignin, organic solvent lignin, sulfite lignin (also known as sulfonic acid lignin or lignosulfonate), and / or lignocellulosic biomass.

[0083] The lignin can contain sulfur or can be substantially sulfur-free. The lignin can be a particulate material having an average particle size greater than or equal to 5 micrometers (μm), optionally greater than or equal to 10 μm, optionally greater than or equal to 15 μm, and less than or equal to 500 μm, optionally less than or equal to 250 μm, optionally less than or equal to 150 μm, optionally less than or equal to 110 μm, optionally less than or equal to 100 μm, optionally less than or equal to 95 μm, optionally less than or equal to 90 μm, or optionally less than or equal to 25 μm. In embodiments, the lignin can have an average particle size greater than or equal to 5 μm and less than or equal to 25 μm, or optionally greater than or equal to 5 μm and less than or equal to 15 μm. The lignin can be subjected to a grinding method (e.g., jet milling) to obtain a desirable average particle size.

[0084] The lignin can be present in the reaction mixture for forming the polyurethane material in a mass ratio greater than or equal to 30 PHR, optionally greater than or equal to 40 PHR, optionally greater than or equal to 50 PHR, optionally greater than or equal to 60 PHR, optionally greater than or equal to 70 PHR, or optionally greater than or equal to 80 PHR, and less than or equal to 90 PHR. The lignin can account for greater than or equal to 30%, optionally greater than or equal to 40%, optionally greater than or equal to 50%, optionally greater than or equal to 60%, optionally greater than or equal to 70%, optionally greater than or equal to 80%, and less than or equal to 90% by weight of the polyurethane material.

[0085] A polyisocyanate is a polyfunctional isocyanate containing at least two isocyanate groups (-N=C=O groups or NCO groups). For example, polyisocyanates can include diisocyanates, triisocyanates, tetraisocyanates, etc. The isocyanate groups in the polyisocyanate are formulated to react with the hydroxyl groups on the polyol and / or lignin to form urethane bonds (-NH-(C=O)-O-) therebetween, thereby forming a polyurethane material. Examples of polyisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a mixture of diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate (crude MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and combinations thereof.

[0086] The polyol, lignin, and optional crosslinker each contain isocyanate-reactive groups, namely hydroxyl groups (or -OH groups). As is well known in the art, the isocyanate index of the reaction mixture for forming a polyurethane material is the ratio of the total number of isocyanate groups in the polyisocyanate to the total number of isocyanate-reactive groups in the reaction mixture (i.e., the polyol, lignin, and optional crosslinker) multiplied by 100. The polyisocyanate can be included in the reaction mixture for forming a polyurethane material in an amount such that the isocyanate index of the reaction mixture is greater than or equal to 50, optionally greater than or equal to 75, or optionally greater than or equal to 100, and less than or equal to 150, optionally less than or equal to 125, or optionally less than or equal to 110. The amount of the polyisocyanate included in the reaction mixture for forming a polyurethane material can be selected to provide a desired density and / or stiffness to the polyurethane material.

[0087] The catalyst is formulated to accelerate the reaction between the polyol, lignin, and polyisocyanate and the formation of covalent bonds, thereby accelerating the formation of the polyurethane material. In embodiments where the reaction mixture for forming the polyurethane material contains an optional blowing agent and the polyurethane material is a polyurethane foam, the catalyst can be formulated to accelerate the reaction between the polyisocyanate and the blowing agent (such as water) to generate gas bubbles (such as CO2 bubbles) in the polyurethane material. The catalyst includes metal catalysts and amine catalysts. The metal catalyst can include organometallic-containing catalysts and can include mercury, lead, tin, bismuth, potassium, zinc, or combinations thereof. Examples of metal catalysts include dibutyltin dilaurate, stannous octoate, potassium octoate, and combinations thereof. In an embodiment, the metal catalyst includes dibutyltin dilaurate. The metal catalyst can be present in the reaction mixture for forming the polyurethane material in a mass ratio greater than or equal to 0.5 PHR, optionally greater than or equal to 1 PHR, or optionally greater than or equal to 1.5 PHR, and less than or equal to 4 PHR, optionally less than or equal to 3 PHR, or optionally less than or equal to 2 PHR. The amine catalyst can include tertiary amines. Examples of tertiary amine catalysts include diethylenetriamine (DETA), dimethylcyclohexylamine (DMCHA), dimethylethanolamine (DMEA), triethanolamine (TEA), and combinations thereof. The amine catalyst can be present in the reaction mixture for forming the polyurethane material in a mass ratio greater than or equal to 0.1 PHR, optionally greater than or equal to 0.3 PHR, or optionally greater than or equal to 0.5 PHR, and less than or equal to 2 PHR, or optionally less than or equal to 1 PHR.

[0088] An optional surfactant can be included to help stabilize the physical structure of the polyurethane material. Examples of surfactants include silicone-containing materials, such as polyether siloxanes. When present, the surfactant can be present in the reaction mixture for forming the polyurethane material in a mass ratio greater than or equal to 0.5 PHR, optionally greater than or equal to 1 PHR, or optionally greater than or equal to 1.5 PHR, and less than or equal to 6 PHR, optionally less than or equal to 5 PHR, or optionally less than or equal to 4 PHR.

[0089] An optional crosslinking agent may be included to help stabilize the polyurethane material and help form crosslinks within the polyurethane material, thereby increasing the rigidity of the material. Examples of crosslinking agents include diols and polyols having a molecular weight greater than or equal to 50 grams per mole (g / mol) and less than or equal to 300 g / mol. Examples of crosslinking agents include low molecular weight diols, polyols, and / or polyamines, including glycerin, glycerol, glycerol propoxylate, diethanolamine (DEA), triethanolamine (TEA), trimethylolpropane, ethylene glycol, propylene glycol, dimethylthiotoluenediamine (DMTDA), 1,4-butanediol, diethyltoluenediamine (DETDA), and combinations thereof. When present, the optional crosslinking agent may be present in the reaction mixture used to form the polyurethane material in a mass ratio greater than or equal to 1 PHR, optionally greater than or equal to 3 PHR, or optionally greater than or equal to 5 PHR, and less than 10 PHR, or optionally less than or equal to 7 PHR.

[0090] In an embodiment, the reaction mixture used to form the polyurethane material may include less than 10 PHR, or optionally less than 7 PHR, or optionally less than 5 PHR of diols, polyols, and / or polyamines having a molecular weight less than or equal to 300 g / mol.

[0091] An optional blowing agent may be included in embodiments where the polyurethane material includes a polyurethane foam. In such cases, the optional blowing agent may be included to form or assist in forming gas bubbles within the polyurethane material. The blowing agent may be a chemical blowing agent that reacts with one or more components in the reaction mixture (such as a polyisocyanate) to form gas bubbles, or a physical blowing agent that forms gas bubbles in the polyurethane material itself. Examples of chemical blowing agents include water. Examples of physical blowing agents include gases (such as liquefied carbon dioxide), volatile liquids having a boiling point less than or equal to 75 degrees Celsius (°C), optionally less than or equal to 60 °C, or optionally less than or equal to 50 °C, and combinations thereof. Examples of volatile liquids that can be used as physical blowing agents include hydrocarbons having 4 or 5 carbon atoms (such as cyclopentane, isopentane, and / or n-pentane, hydrofluorocarbons, hydrochlorofluorocarbons), oxygen-containing compounds (such as methyl formate and / or dimethoxymethane), hydrochlorocarbons (such as dichloromethane and / or 1,2-dichloroethane), ketones (such as acetone), aldehydes (such as methylal), and combinations thereof. When present, the optional blowing agent may be present in the reaction mixture used to form the polyurethane material in a mass ratio greater than or equal to 0.1 PHR, optionally greater than or equal to 0.5 PHR, or optionally greater than or equal to 1 PHR, and less than 5 PHR, or optionally less than or equal to 2 PHR.

[0092] Optional additives may be included to impart certain desirable properties to the polyurethane material. In embodiments, the optional additives may include flame retardants, viscosity modifiers, antimicrobial agents, pigments, fragrances, antioxidants (antioxidative degradation stabilizers), UV light stabilizers, or combinations thereof. Examples of flame retardants include lignosulfonate compounds, phosphorus-containing compounds, bromine-containing compounds, polyamide compounds, polyetherimide compounds, aluminum-containing compounds, magnesium-containing compounds, and combinations thereof. Examples of viscosity modifiers include diesters. When present, the optional additives may be present in the reaction mixture for forming the polyurethane material in a mass ratio greater than or equal to 1 PHR, optionally greater than or equal to 2 PHR, optionally greater than or equal to 5 PHR, or optionally greater than or equal to 10 PHR, and less than 25 PHR, or optionally less than or equal to 15 PHR.

[0093] Method

[0094] The polyurethane material can be prepared by preparing a reaction mixture comprising a polyol, lignin, polyisocyanate, catalyst, optional surfactant, optional crosslinker, optional blowing agent, and optional additives. The reaction mixture can be prepared by the following steps: (i) forming a polyol mixture comprising the polyol and lignin, (ii) introducing the catalyst and optional blowing agent into the polyol mixture to form an intermediate mixture, and then (iii) introducing the polyisocyanate into the intermediate mixture to form the polyurethane material. In embodiments, the polyol mixture may further comprise an optional surfactant, an optional crosslinker, and / or an optional additive, and these components may be introduced into the polyol mixture simultaneously or subsequently with the polyol and lignin before forming the intermediate mixture. The mass ratio of lignin to polyol (lignin: polyol) in the polyol mixture may be greater than 3:7 and less than or equal to 9:1.

[0095] The polyol mixture is formed by mechanically mixing the polyol and lignin together, for example, using a centrifugal mixer, a disperser (e.g., using disk blades), or a paddle mixer, operating at a speed of about 1000 revolutions per minute (rpm) to about 3000 rpm or about 2000 rpm for a duration of about 5 minutes to about 1 hour. After the polyol and lignin are mixed together, the polyol mixture may be allowed to "soak" for a duration greater than or equal to 1 hour, optionally greater than or equal to 24 hours, or optionally greater than or greater than 1 week, and less than or equal to 2 years. The optional surfactant, optional crosslinker, and / or optional additive may be added to the polyol mixture before or after soaking. The polyol mixture may be mixed at a temperature greater than or equal to 50 °C and less than or equal to 75 °C. During the mixing process, heat may be generated in the polyol mixture, for example, by heat generated due to friction during the mixing process itself, or by externally applied heat, such as by heating the polyol mixture in an oven.

[0096] An intermediate mixture is formed by mechanically mixing a catalyst and an optional blowing agent into a polyol mixture, for example using a centrifugal mixer, a disperser (e.g., using disk blades), or a paddle mixer, operating at a speed of about 1000 revolutions per minute (rpm) to about 3000 rpm or about 2000 rpm for a duration of about 30 seconds to about 1 hour.

[0097] A final reaction mixture is formed by mechanically mixing a polyisocyanate into the intermediate mixture, for example using a centrifugal mixer, a disperser (e.g., using disk blades), or a paddle mixer, operating at a speed of about 1000 revolutions per minute (rpm) to about 3000 rpm or about 2000 rpm for a duration of about 1 second to about 1 minute. After mixing the polyisocyanate into the intermediate mixture, the reaction mixture can be transferred to a mold or other container and allowed to cure and solidify to form a polyurethane material.

[0098] Experiment

[0099] Polyurethane foams are prepared from different reaction mixtures, and the density and compression force deflection (CFD) of the polyurethane foams are measured. Dibutyltin dilaurate (DBTDL) is used as a metal catalyst and purchased from Sigma - Aldrich. 380 and 1168 are used as polyols and provided by BASF. VORASRF DC 6070 is used as a surfactant and provided by DOW. E 10 is used as a tertiary amine catalyst and provided by Evonik. Mondur MR Light is used as a polyisocyanate and provided by Covestro. Lignin is provided by SweetWater Energy Inc. and used as received, rather than jet - milled to an average particle size of 10 μm. Max 100 Long FlackTek cups are purchased from Fischer Scientific. As published by BASF, 380 has a nominal functionality of 3, a hydroxyl value of 24.0 - 26.0 mg KOH / g, a nominal molecular weight of 6500 daltons, a viscosity of 1370 cP at 77 degrees Fahrenheit (°F), and up to 0.05 wt% water. 1168 has a nominal functionality of 4, a hydroxyl value of 285 - 315 mg KOH / g, a nominal molecular weight of 740 daltons, a viscosity of 1800 cP at 77 degrees Fahrenheit (°F), and up to 0.10 wt% water.

[0100] Density measurement: For Comparative Example 2 and Examples 3 to 6: Rectangular blocks with dimensions of approximately 25 mm in height x 50 mm in width x 50 mm in length were cut from the main-cured foam blocks. The actual measured values were confirmed using a digital caliper on a single foam sample basis. For Comparative Example 1: A cross-section approximately 10 mm thick was cut from the main-cured foam block. After cutting, a disc with a diameter of 30 mm was axially punched out from the 10-mm thick cross-section using a 30-mm die cutter to form a cylindrical foam piece with dimensions of approximately 10 mm x 30 mm. The actual measured values were confirmed using a digital caliper on a single foam sample basis. Then, the cut foam blocks were weighed using a laboratory balance to calculate the density of a single foam.

[0101] Compression force deflection (25%) measurement: The compression force deflection test was carried out in accordance with ASTM D1621 using a deformation value of 25%. The test was performed on an Instron equipped with a fixed rectangular bottom platform and a movable compression attachment purchased from Instron. The foam blocks cut from Comparative Example 1 and Examples 2 to 5 for density calculation were used to determine the CFD 25％ . The sample was compressed to a 25% deformation and the maximum force was measured. The CFD value was determined by dividing the maximum force at 25% deformation by the cross-sectional surface area of the sample. 25％ value.

[0102] Comparative Example 1: Synthesis of Base Foam 1

[0103] A polyol mixture containing 380 (20.0 g, 100 phr) and VORASRF DC 6070 (400 mg, 2 phr) was prepared in a Max 100 Long FlackTek cup and mixed in a FlackTec mixer at 2000 rpm for 5 minutes. Then, DBTDL (400 mg, 2 phr), E 10 (100 mg, 0.5 phr) and deionized water (200 mg, 1 phr) were added to the polyol mixture and mixed at 2000 rpm for 1 minute using a disperser blade attached to a overhead mixer to form an intermediate mixture. Mondur MR Light (4.15 g, 1 equivalent wrt polyol) was added to the intermediate mixture in the cup and mixed at 2000 rpm for 15 seconds using the same overhead mixer to form a polyurethane foam. The foam was allowed to stand at room temperature for 72 hours before density measurement on 3 foam samples. The resulting polyurethane foam had a density of 130 kg / m 3 ³.

[0104] Comparative Example 2: Synthesis of Base Foam 2

[0105] Prepare a polyol mixture containing 1168 (8.0 g, 100 phr) and VORASRF DC 6070 (120 mg, 1.5 phr) in a Max 100 Long FlackTek cup and mix in a FlackTec mixer at 2000 rpm for 3 minutes. Then, add DBTDL (160 mg, 2 phr), E 10 (40 mg, 0.5 phr) and deionized water (120 mg, 1.5 phr) to the polyol mixture and mix at 2000 rpm for 3 minutes using a disperser blade attached to a overhead mixer to form an intermediate mixture. Add Mondur MR Light (8.21 g, 1.1 equivalents wrt polyol) to the intermediate mixture in the cup and mix at 2000 rpm for 5 seconds using the same overhead mixer to form a polyurethane foam. Allow the foam to stand at room temperature for at least 72 hours before measuring the density and compression force deflection of 3 foam samples. The resulting polyurethane foam has a density of 79 kg / m 3 and a CFD 25％ value of 623 kPa.

[0106] Example 3: Synthesis of a Base Foam with 50 phr Lignin

[0107] Prepare a polyol mixture containing 380 (10.0 g, 50 phr), lignin (10.00 g, 50 phr) and VORASRF DC 6070 (800 mg, 4 phr) in a Max 100 Long FlackTek cup and mix in a FlackTec mixer at 2000 rpm for 3 minutes. Then, add DBTDL (400 mg, 2 phr) and E 10 (100 mg, 0.5 phr) to the polyol mixture and mix in a FlackTek mixer at 2000 rpm for 8 minutes to form an intermediate mixture. Immediately after forming the intermediate mixture, add Mondur MR Light (5.64 g, 0.75 equivalents wrt polyol) to the intermediate mixture in the cup and mix at 2000 rpm for 10 seconds using the same FlackTek mixer to form a polyurethane foam. Allow the foam to stand at room temperature for at least 72 hours before measuring the density and compression force deflection of 3 foam samples. The resulting polyurethane foam has a density of 215 ± 5 kg / m 3 and a CFD 25％ value of 140 ± 9 kPa.

[0108] Example 4: Synthesis of a Base Foam with 50 phr Lignin

[0109] Prepare a polyol mixture containing 380 (10.0 g, 50 phr), lignin (10.00 g, 50 phr) and VORASRF DC 6070 (800 mg, 4 phr) in a Max 100 Long FlackTek cup and mix in a FlackTec mixer at 2000 rpm for 3 minutes. Then, add DBTDL (400 mg, 2 phr) and E 10 (100 mg, 0.5 phr) to the polyol mixture and mix in a FlackTek mixer at 2000 rpm for 8 minutes to form an intermediate mixture. Immediately after forming the intermediate mixture, add Mondur MR Light (5.64 g, 1 equivalent wrt polyol) to the intermediate mixture in the cup and mix with the same FlackTek mixer at 2000 rpm for 10 seconds to form a polyurethane foam. Let the foam stand at room temperature for at least 72 hours before measuring the density and compression force deflection of 3 foam samples. The resulting polyurethane foam has a density of 173 ± 19 kg / m 3 and a CFD 25％ value of 135 ± 1 kPa.

[0110] Example 5: Synthesis of a base foam with 60 phr lignin

[0111] Prepare a polyol mixture containing 380 (8.0 g, 40 phr), lignin (12.00 g, 60 phr) and VORASRF DC 6070 (800 mg, 4 phr) in a Max 100 Long FlackTek cup and mix in a FlackTec mixer at 2000 rpm for 3 minutes. Then, add DBTDL (400 mg, 2 phr) and E 10 (100 mg, 0.5 phr) to the polyol mixture and mix in a FlackTek mixer at 2000 rpm for 8 minutes to form an intermediate mixture. Immediately after forming the intermediate mixture, add Mondur MR Light (5.64 g, 0.75 equivalent wrt polyol) to the intermediate mixture in the cup and mix with the same FlackTek mixer at 2000 rpm for 10 seconds to form a polyurethane foam. Let the foam stand at room temperature for at least 72 hours before measuring the density and compression force deflection of 3 foam samples. The resulting polyurethane foam has a density of 216 ± 3 kg / m 3 and a CFD 25％ value of 624 ± 54 kPa.

[0112] Example 6: Synthesis of a Base Foam with 60 phr Lignin

[0113] Prepare a polyol mixture containing 380 (8.0 g, 40 phr), lignin (12.00 g, 60 phr), and VORASRF DC 6070 (800 mg, 4 phr) in a Max 100Long FlackTek cup and mix in a FlackTec mixer at 2000 rpm for 3 minutes. Then, add DBTDL (400 mg, 2 phr) and E 10 (100 mg, 0.5 phr) to the polyol mixture and mix in a FlackTek mixer at 2000 rpm for 8 minutes to form an intermediate mixture. Immediately after forming the intermediate mixture, add Mondur MR Light (5.64 g, 1 equivalent wrt polyol) to the intermediate mixture in the cup and mix with the same FlackTek mixer at 2000 rpm for 10 seconds to form a polyurethane foam. Let the foam stand at room temperature for at least 72 hours before measuring the density and compression force deflection of 3 foam samples. The resulting polyurethane foam has a density of 185 ± 15 kg / m 3 and a CFD 25％ value of 408 ± 4 kPa.

[0114] Example 7: Synthesis of a Base Foam with Two Polyols and 50 phr Lignin

[0115] Prepare a polyol mixture containing 380 (9.0 g, 45 phr) and 1168 (1.0 g, 5 phr) in a Max 100Long FlackTek cup and mix in a FlackTec mixer at 2000 rpm for 2 minutes. Then, add Sunburst hydrolyzed lignin (10.00 g, 50 phr) and VORASRF DC 6070 (800 mg, 4 phr) to the polyol mixture and mix again at 2000 rpm for 3 minutes. Add DBTDL (400 mg, 2 phr) and E 10 (100 mg, 0.5 phr) was added to the polyol mixture and mixed in a FlackTek mixer at 2000 rpm for 8 minutes to form an intermediate mixture. Immediately after forming the intermediate mixture, Mondur MR Light (8.17 g, 1.0 equivalent wrt polyol) was added to the intermediate mixture in the cup and mixed in the same FlackTek mixer at 2000 rpm for 10 seconds to form a polyurethane foam. The foam was allowed to stand at room temperature for at least 72 hours before density and compression force deflection measurements were taken on 3 foam samples. The resulting polyurethane foam had a density of 187 kg / m 3 and a CFD of 323 kPa 25％ value.

[0116] Example 8: Synthesis of a Base Foam with a Crosslinker and 50 phr Lignin

[0117] A polyol mixture containing 380 (10.0 g, 50 phr), Sunburst hydrolyzed lignin (10.00 g, 50 phr), diethanolamine (1.0 g, 5 phr), and VORASRF DC 6070 (800 mg, 4 phr) was prepared in a Max 100Long FlackTek cup and mixed in a FlackTek mixer at 2000 rpm for 3 minutes. Then, DBTDL (400 mg, 2 phr) and E 10 (100 mg, 0.5 phr) were added to the polyol mixture and mixed in a FlackTek mixer at 2000 rpm for 8 minutes to form an intermediate mixture. Immediately after forming the intermediate mixture, Mondur MR Light (10.10 g, 1.0 equivalent wrt the hydroxyl groups of the polyol and diethanolamine) was added to the intermediate mixture in the cup and mixed in the same FlackTek mixer at 2000 rpm for 10 seconds to form a polyurethane foam. The foam was allowed to stand at room temperature for at least 72 hours before density and compression force deflection measurements were taken on 3 foam samples. The resulting polyurethane foam had a density of 158 kg / m 3 and a CFD of 267 kPa 25％ value.

[0118] The foregoing description is merely exemplary and is in no way intended to limit the disclosure, its application, or uses. The broad teachings of the disclosure can be implemented in a variety of forms. Therefore, although the disclosure includes specific examples, the true scope of the disclosure should not be so limited since other modifications will become apparent upon a study of the drawings, the specification, and the following claims. It should be understood that one or more steps within a method may be implemented in a different order (or concurrently) without altering the principles of the disclosure. In addition, although each of the embodiments has been described above as having certain features, any one or more of the features described with respect to any one embodiment of the disclosure may be implemented in and / or combined with any other embodiment, even if not explicitly described in that combination. In other words, the described embodiments are not mutually exclusive, and the interchanging of one or more embodiments is still within the scope of the disclosure.

[0119] The terms used herein are for the purpose of describing exemplary embodiments only and are not intended to be limiting. Unless the context clearly dictates otherwise, the singular forms “a,” “an,” and “the” used herein are also intended to include the plural forms. The terms “comprising,” “including,” and “having” are inclusive and therefore specify the presence of stated features, elements, compositions, steps, integers, operations, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or combinations thereof. Although the open-ended terms “comprising,” “including,” and “having” are to be understood as non-limiting terms used to describe and claim the various embodiments herein, in some instances these terms may alternatively be understood as more restrictive and limiting terms, such as “consisting of” or “consisting essentially of.” Accordingly, for any given embodiment that lists compositions, materials, components, elements, ingredients, features, integers, operations, and / or method steps, the disclosure also explicitly includes embodiments consisting of, or consisting essentially of, these listed compositions, materials, components, elements, ingredients, features, integers, operations, and / or method steps. In the case of “consisting of,” the alternative embodiment does not include any additional compositions, materials, components, elements, ingredients, features, integers, operations, and / or method steps, while in the case of “consisting essentially of,” such an embodiment does not include any additional compositions, materials, components, elements, ingredients, features, integers, operations, and / or method steps that materially affect the basic and novel features, but may include any compositions, materials, components, elements, ingredients, features, integers, operations, and / or method steps that do not materially affect the basic and novel features.

[0120] The phrase “at least one of A, B, and C” used herein should be construed to mean a logical (A or B or C) using a non-exclusive logical OR and should not be construed to mean “at least one of A, at least one of B, and at least one of C.”

[0121] Unless otherwise specified, the terms "composition" and "material" as used herein are used interchangeably to generally refer to a substance that contains at least a preferred chemical component, element, or compound but may also contain additional elements, compounds, or substances, including trace impurities. A "composition or material based on X" generally refers to a composition or material in which "X" is the single largest component by weight percentage (%) of the composition or material. This can include compositions or materials having greater than 50 wt% X, and can also include compositions or materials having less than 50 wt% X, provided that X is the single largest component based on the total weight of the composition or material. When a composition or material is referred to as being "substantially free of" a substance, the composition or material may contain less than 5 wt%, optionally less than 3 wt%, optionally less than 1 wt%, or optionally less than 0.1 wt% of the substance by weight.

Claims

1. A polyurethane material, which comprises the reaction product of the following substances: A polyol, the polyol comprising an amphiphilic polyoxyalkylene copolymer having at least two terminal primary hydroxyl groups, the amphiphilic polyoxyalkylene copolymer comprising a hydrophilic oxyalkylene group covalently bonded to a hydrophobic oxyalkylene group; Lignin; A catalyst; A polyisocyanate; Optionally, a surfactant, the surfactant including a silicone-containing material; Optionally, a blowing agent; and Optionally, an additive, the additive including a flame retardant, a viscosity modifier, an antimicrobial agent, a pigment, a fragrance, an antioxidant, a UV light stabilizer, or a combination thereof.

2. The polyurethane material according to claim 1, wherein the lignin is a particulate material having an average particle size greater than or equal to 5 microns and less than or equal to 25 microns.

3. The polyurethane material according to claim 1, wherein the lignin accounts for more than 50% by weight of the polyurethane material, and wherein the lignin is uniformly distributed throughout the polyurethane material.

4. The polyurethane material according to claim 1, wherein the lignin is a natural plant product, kraft lignin, soda lignin, organosolv lignin, sulfite lignin, lignocellulosic biomass, or a combination thereof, and wherein the lignin has not been subjected to propoxylation, chemical grafting, heat treatment, hydrolysis, microwave radiation, or a combination thereof.

5. The polyurethane material according to claim 1, wherein the amphiphilic polyoxyalkylene copolymer comprises a copolymer of ethylene oxide and propylene oxide.

6. The polyurethane material according to claim 1, wherein the polyol comprises a first amphiphilic polyoxyalkylene copolymer having a functionality greater than or equal to 2 and less than or equal to 3, a nominal molecular weight greater than or equal to 6000 daltons and less than or equal to 7000 daltons, and a hydroxyl value greater than or equal to 20 mg potassium hydroxide / gram and less than or equal to 30 mg potassium hydroxide / gram.

7. The polyurethane material according to claim 6, wherein the polyol further comprises a second amphiphilic polyoxyalkylene copolymer having a functionality greater than or equal to 4 and less than or equal to 6, a nominal molecular weight greater than or equal to 180 daltons and less than or equal to 1000 daltons, and a hydroxyl value greater than or equal to 200 mg potassium hydroxide / gram and less than or equal to 400 mg potassium hydroxide / gram.

8. The polyurethane material according to claim 1, wherein the polyisocyanate includes toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof, and wherein the catalyst includes a metal-containing catalyst and a tertiary amine catalyst.

9. The polyurethane material according to claim 1, which further comprises a crosslinking agent, the crosslinking agent comprising a polyol having a molecular weight greater than or equal to 50 g / mol and less than or equal to 300 g / mol.

10. The polyurethane material according to claim 1, wherein the polyurethane material is a polyurethane foam, and the polyurethane foam has a density of greater than or equal to 150 kg / m³ and less than or equal to 250 kg / m³ and a compression force deflection of greater than or equal to 100 kPa and less than or equal to 800 kPa.

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