Production of wood adhesives and boards from lignocellulosic biomass

Abstract

Biomass products containing protected lignocellulosic material are described. In a process for making a biomass product, a lignocellulosic material is combined with a protecting reagent in a solvent to form a biomass dispersion, lignin in the lignocellulosic material in the biomass dispersion is reacted with the protecting reagent in the presence of an acid catalyst or a base catalyst under reaction conditions to protect lignin (3-0-4 linkages forming a protected biomass dispersion, optionally neutralizing the protected biomass dispersion and removing all or a portion of the solvent from the protected biomass dispersion to yield a biomass product containing protected lignocellulosic material. The resulting biomass product containing protected lignocellulosic material may itself be used in a wood adhesive for composite article manufacture, either as a solid or a liquid adhesive composition. The biomass product may be used as the resin component in a conventional wood adhesive composition or the biomass product itself may be formed directly into boards.

Description

[0001] Patent Application Docket 24-41-FF01 PRODUCTION OF WOOD ADHESIVES AND BOARDS FROM LIGNOCELLULOSIC BIOMASS

[0002] Cross-reference to Related Applications

[0003] [001) This application claims priority to US patent application 63 / 738, 393, filed December 23, 2024, which is incorporated by reference.

[0004] Background

[0005]

[0002] Composite wood products are routinely used to construct walls, floors, roofs, cabinets, furniture, architectural moldings, among other products. Composite wood products are often composite wood panels, both structural and non- -nonstructural panels. Common composite wood panel products are, far example, plywood, oriented strand board (OSB), particleboard (PB), and fiberboards of different densities e.g., low density fiberboard (LDF), medium density fiberboard (MDF) and high density fiberboard (HDF)). At its most basic, a composite wood product is composed of wood veneers, wood panels, wood blocks, wood fibers, wood chips, wood pa rticles, or wood flour and a wood adhesive. Common wood adhesives are formaldehyde-based resins, such as urea- formaidehyde (LIF), mefohiine-fi>r mdshyde (MF), melamine -urea -ftirmaldehydt? ( UF) rasorcinoi- formaldehyde (RF), phano^resorcl i-formaldehyde (PRE) and phenol-formaldehyde (PF) resins, and to some extent, formaldehyde-free resins, such as polymeric methylene diphenyl diisocyanate (pMDI). The formaldehyde- -based resins are thermoset resins and contain a certain amount of free formaldehyde. Upon curing, formaldehyde may react with components of the resin or evaporate from the panels. There has been interest in moving to bio-based adhesives to significantly reduce or even eliminate formaldehyde-based resins in the manufacture of composite wood products.

[0006]

[0003] Lignin is a class of naturally occurring polymer which acts as a binder in wood and other lignocellulosic plants. Lignin is, therefore, a renewable resource. The following linkages have been reported in lignin.

[0007]

[0008] See Solihst, N. N.; Sari, ER; Falah, E; Lsmayati, M.; Luhis, M. A.ft.j Fatriasari, W<; Santoso, E. B.;: Syafii, W. Lignin as an Active Biomsteriai: A Review. 1 Syiva Lestari 2021, S, 1-22.Patent Application Docket 24-41-FF01

[0004] Lignin units attached to adjacent units in ring positions 2, 3, 5, or 6 (see formula below) are referred to as “condensed units,'' and consequently units lacking connection to other units in these positions are ''uncondensed." See Lundquist, K„ and Parkas, J. " Different types of phenolic units in lignins," Sloites. 6(2), 528-926, (2011); Yang, G„ Gong, Z;, Luo,. et al. Bonding wood with biomass powders as wood adhesives, Nature 621, 511-S15 (2023).

[0009] Y C

[0010]

[0011] OR"

[0012] According to Li Shuai’s group, "different condensation degrees, as reflected, inversely, by the molar yields of the resulting aromatic monomers from their hydrogenolysis." Yang, G., Gong, Z., Luo, X. et al. Bonding wood with uncondensed lignins as adhesives. Nature 621, 511–515 (2023).

[0013] (005) Overall, as shown in the figure above, uncondensed or partially condensed lignin has more available active sites, specifically on the 2,3,5,6 position of the aromatic ring. Condensed lignin will have reacted with a majority of these active sites likely due to the condensation between the β-O-4 aryl ether and the various positions of the aromatic ring. This causes the loss of the primary hydroxyl groups associated with the β-O-4 aryl ether positions. These changes can be observed by HSQC-NMR and CNMR when comparing lignin extracted with and without the use of a protecting agent. This can be further evidenced by GPC, when comparing lignin extracted with and without the use of a protecting group. Lastly, according to Li Shuai (WO2023 / 208015 A1), different degrees of condensation can be observed by monomer yield after hydrogenolysis, where higher condensed lignin results in lower monomer yield,

[0014] (006) Lignin has been proposed as an ecofriendly alternative for wood adhesives used to produce composite wood products. Associating lignin with the various resin systems used in known wood adhesives has been reported. See, for example, WO 2019 / 068180 Al. These approaches, however, have utilized condensed lignin. With its complex structure when lignin is extracted from a plant source, lignin undergoes a condensation reaction, forming carbon-carbon bonds making its structure even more complex and the condensed lignin less reactive. Condensed lignin is more difficult to process and, with its decreased reactivity, has less utility and promise to be an ecofriendly alternative for wood adhesives.

[0015] (007) Separation of lignin from biomass, for use in wood adhesives, is widely reported. One method involves the protection of β-O-4 linkages in lignin, with an aldehyde, to farm acetals. WOPatent Application Docket 24-41-FF01 2023 / 208015 Al, for example, describes a method for derivatizing and extracting lignin from a biomass and using the extracted, modified lignin as wood adhesive. The method derlvatizes the lignin prior to extraction by reacting lignin in the biomass with an agent wh ich is one or more of formaldehyde, paraformaldehyde, acetaldehyde, paraldehyde, para-acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, furfural, acetone, and butanone to modify the lignin. This protects the β-O-4 ether linkage from cleavage during extraction of the lignin and prevents formation of carbon -carban bonds. This method prevents condensation of lignin during high temperature and low or high pH extractions. The resulting protected lignin is seif-crosslinking upon exposure to heat and / or acid. However, the current: method of extraction is costly, involving hazardous solvents and multiple filtration and separation stages. Additionally, the output of protected lignin product, relative to the batch size, is extremely low,

[0016]

[0008] There remains a need for improved production of wood composite materials which focus on bio-based adhesive and minimizes or even eliminates added wood adhesives. This invention answers that need.

[0017] Summary of the Invention

[0018]

[0009] The invention relates to processes for making a biomass product. A process of the invention comprises the steps of combining lignocellulosic material with a protecting reagent in a solvent to form a biomass dispersion, reacting lignin in the lignocellulosic material in the biomass dispersion with a protecting reagent in the presence of an acid catalyst or a base catalyst under reaction conditions to protect lignin β-O-4 linkages in the lignocellulosic material to form a protected biomass dispersion, optionally neutralizing the protected biomass dispersion, and removing all or a portion of the solvent from the protected biomass dispersion to yield a biomass product containing protected lignocsllulssic material. As used herein, a "protected biomass" a "protected: biomass dispersion", and a "biomass product containing protected iignocellulosic material" refers to a biomass, a dispersion, or a lignocellulosic material prepared using a process of the invention having the step of reacting lignin in a biomass with a protecting reagent. A process of the invention may include certain further embodiments alone or in combination, such as,

[0019] • the reaction conditions are sufficient to also hydrolyze Iignocellulosic material in the biomass dispersion,

[0020] • further comprising, prior to or during the reaction step, the step of sonicating the biomass dispersion to break down the lignocellulosic material,

[0021] • a t least a portion of the solvent is removed from the protected biomass,

[0022] • the solvent is removed from the protected biomass,Patent Application Docket 24-41-FF01 • further comprising, prior to the solvent removal step, the step of mixing the protected biomass with an additional solvent,

[0023] • the solvent is water,

[0024] • the protecting reagent is selected from the group of an aldehyde, a ketone, a carbonate, and a boric acid and a boronic acid,

[0025] • the reacting step comprises adding a catalyst to the biomass dispersion and heating to a temperature where the protecting reagent reacts with the lignin β-O-4 linkages in the lignocellulosic material,

[0026] • the process includes the step of neutralizing: the protected biomass, and

[0027] • for some protecting reagents, post-protection processing of the protected biomass may deprotect some or all of the β-O-4 or other hydroxyl functionality in the protected biomass without loss of its adhesive or other properties,

[0028]

[0010] The invention also relates to a biomass product prepared by a process of the invention. The invention further provides compositions comprising 10 to 70 wt.% of the biomass product containing protected lignocellulosic material, up to 90 wt.% solvent, and up to 30 wt.% of a catalyst or reactant for deprotecting, ring opening, or crosslinking with at least the protected β-O-4 linkages.

[0029]

[0011] The invention also relates to a process of making a board comprising the steps of forming a biomass product containing protected lignocellulosic material into a mat and pressing the mat at a pressure and temperature sufficient to form a board. A board made by such a process is another aspect of the invention.

[0030] [Q12] The invention further provides wood adhesives comprising 10-70 wt.% of a biomass product containingprotected iignoceiluiosic material, 0-90 wt% solvent, and 1-30 wt.% of an acid catalyst, and 0-50 wt% additives. Another aspect of the invention includes processes: for manufacturing a composite article comprising the steps of applying such a wood adhesive to at least one surface of a substrate to form a coated substrate and pressing the substrate at an elevated temperature and for a time sufficient to cure the coated substrate and form the composite article. Processes of the invention may be used fa manufacture composite articles such as plywood, a laminated veneer layer (LVL) product, laminated glulam beam, mass timber, oriented strand board (OSB), cross-laminated timber (CLT), particle board, medium density fiberboard (MDF), impregnated paper, or paper board.

[0031]

[0013] Unlike prior lignin-based wood adhesives processes that require extraction and purification of lignin, the invention performs a protective reaction within the whole lignocellulosic biomass, retaining cellulose and hemicellulose during modification and use. This one-pot, non-extractive process advantageously eliminates multiple solvent-intensive separation stages, reducing cost, energy use, and environmental impact. Contrary to expectations that unremoved biomassPatent Application Docket 24-41-FF01 constituents would interfere with Sighin reactivity and adhesive strength, the inventors discovered that these components enhance network formation, serving as scaffolds that promote cohesive crosslinking during curing. As a result, the directly protected biomass product yields adhesives and boards exhibiting mechanical performance equal to or superior to systems made from extracted lignin. The invention therefore provides an unexpectedly efficient and high-performing route to renewable, formaldehyde-reduced wood adhesives and composite materials.

[0032] Description of the Invention

[0033] (014] Starting from a lignocellulosic material, the invention provides processes for making a biomass product containing protected lignocellulosic material The biomass product may be used in a composition, such as a wood adhesive, and in processes for making a board. Processes of the invention utilize the entire biomass of the lignoceiiulosic material. In a process of the invention, β-O-4 linkages in the lignin contained in the lignocellulosic material are protected. Separation stages, such as separation of lignin from cellulose and hemicellulose, are omitted, thereby significantly reducing: cost and hazard of the operation.

[0034]

[0015] Preparation of a Biomass Product Containing Protected Lignocellulosic Material

[0035]

[0016] In a process for making a biomass product according to the invention, a lignocellulosic material is combined with a protecting reagent in a solvent to form a biomass dispersion, lignin in the lignocellulosic material in the biomass dispersion is reacted with the protecting reagent in the presence of an acid catalyst or a base catalyst under reaction conditions to protect lignin β-O-4 linkages forming a protected biomass dispersion, optionally neutralizing the protected biomass dispersion and removing all or a portion of the solvent from the protected biomass dispersion to yield a biomass product containing protected lignoceiiulosic material The resulting biomass product containing protected lignocellulosic material may itself be used in a wood adhesive for composite wood manufacture, either as a solid or a liquid adhesive composition. The biomass product may also be used as the resin component in a conventional wood adhesive composition. Or the biomass product itself may be formed directly into boards,

[0036]

[0017] The invention relates to a process for making a biomass product comprising, consists essentially of, or consists of the steps of: combining lignocellulosic material with a protecting reagent in a solvent to form a biomass dispersion, reacting lignin in the lignocellulosic material in the biomass dispersion with a protecting reagent in the presence of an acid catalyst or a base catalyst under reaction conditions to protect lignin β-O-4 linkages in the lignocellulosic material to form a protected biomass dispersion, optionally neutralizing the protected biomass dispersion, and removing all or a portion of the solvent from the protected biomass dispersion to yield a biomass product containing protected Ilgnoceiiuiosic material.Patent Application Docket 24-41-FF01

[0018] A biomass product containing protected lignocellulosic material according to the invention may be made starting from any lignocellulosic material known in the art, such as virgin lignocellulosic materials (plants, bushes, trees, etc.); waste lignocellulosic materials (low value by-products from industrial processes or consumer use); and energy crops. For example, the lignocelluiosic material may come from hard woods, soft woods, wood fibers, wood flour, seeds, endocarps, nuts, nutshells, shell flours, sugarcane bagasse, corn stover, straw, hemp, kudzu, cotton stalk, wheat, bamboo, juts, flax, grasses (switchgra&s, elephant grass and the like)* cereal grasses, coffee grounds, discards (from sawmills, paper mills, construction, and the lite), etc. The lignocellulosic material is preferably from trees such as birch, beech, poplar, cedar, Douglas fir, cypress, firs, juniper, kauri, larch, pine, hemlock, redwood, spruce, yew, eucalyptus, bamboo, and walnut (including walnut shell flour).

[0037] [019 J The lignoceilulosic material may be in the form of chips, flakes, fibers, pellets, granules, shivers, particles, dusts, etc. The lignocellulosic may be cut, sawn, chipped, or ground to a desired form using means known in the art. The lignoceilblosic material may be used “as is" or may be mixed with a solvent, Water, or an aqueous solvent forming a slurry or dispersion for use in subsequent steps of a process of the invention, A slurry or dispersion of lignocellulosic material may be agitated, for example by stirring or sonication, to break down the lignocellulosic material prior to or after combining it with a protecting agent and solvent to form a biomass dispersion.

[0038]

[0020] As mentioned various lignocelldiosic materiais may be used. By way of example, suitable forms of lignocellulosic material include strands in which individual strips are about 20–25 mm wide and about 100–150 mm long; wood particles screened in the range of about 1.6 mm (1 / 16 in) to about 6.4 mm (1 / 4 in); chips and flakes having characteristic dimensions of about 5-50 mm; fibers with typical lengths from about 0.5 mm to about 20 mm; and wood flours or dusts having a median particle size (D50) of about 10–500 μm, with a D90 not exceeding about 1,000 μm.

[0039]

[0021] In some aspects, particularly when preparing adhesive compositions or biomass dispersions, the lignocellulosic material is used in the form of particles having a size of less than about 1 mm. In preferred embodiments, the lignocellulosic material is in the form of a powder having a particle size of less than about 200 mesh. In more preferred embodiments, the lignocellulosic material has a particle size of less than about 325 mesh. Finer particle sizes may facilitate more uniform dispersion of the lignocellulosic material in the biomass dispersion and more effective protection of lignin β-O-4 linkages.

[0040]

[0022] In a process of making a biomass product of the invention, lignocellulosic material is combined with a protecting reagent in a solvent to form a biomass dispersion. The lignocellulosic material in the biomass dispersion may be in the range of 1-50 wt.%, and for example 10-40 wt.%. The protecting reagent acts to protect the β-O-4 linkages of the lignin contained in the biomass byPatent Application Docket 24-41-FF01 forming acetals or other protecting groups. Though they generally do not contain β-O-4 linkages, the hydroxyl groups in the cellulose and other cellulosic material in the lignocellulosic material may also form protected groups, such as acetals. A single protecting reagent or a mixture of protecting reagents may be used. A protecting reagent is typically added in a weight / weight ratio of lignocellulosic material to protecting reagent ranging from 1:0.1 to 1:100, 1:01 to 1:10, 1:01 to 1:5, 1:0.1 to 1:1.5, 0.5:1 to 1:5, 1:1.2 to 0.7:1, 1:0.1 to 1:1, 1:0.1 to 1:0.9, 1:0.25 to 1:0.75, 1:04 to 1:0.6, 1:0.5, 1:07, 1:08, or 1:0.9, unless the protecting reagent is also acting as the solvent.

[0041]

[0023] Suitable protecting reagents known in the art are aldehydes, ketones, carbonates, boric acid, and boronic acids (R-B-(OH)₂), and the like. Such protecting reagents include, but are net limited to, formaldehyde, paraformaldehyde, formaldehyde diethyl acetal, acetaldehyde, paraldehyde, para- acetaldehyde, p-phthalaldehyde, propionaldehyde, butyraldehyde, acetaldehyde, propionaldehyde, isobutyra Idehyde, glyoxylic acid, di aldehyde, cyctaprapanecarboxaidehyde, isobatyraldehyde, pivaldehyde, tolualdehyde, benzaldehyde, 2-hydroxyacettildehyde, 2-chforoatetaldehyd&, 2-bromoacetaldehyde, 2-iodoacetaldehyde, 2-hydroxyacetaldehyde, ethanedial (also known as glyoxal or oxalaldehyde), oxoethanoic acid (also known as 2-oxo-acetic acid or glyoxylic acid), 2,2,2- trichloroacetaldehyde, 4-hydroxy-3,4-dimethoxybenzaidehyde (syringaidehyde), 4-hydoxy-3- msthoxybenzaldehyde (vanillin), -hydroxybenzaldehyde (sslicylaldehyde), 2-chiorohenzaldehyde, 2- bromobenzaldehytie, 2-it>doben2aldehyde, 3-hydroxybenzaldehyde, 3-<:hlorobenzaldeh de, 3- bromobenzaldehyde, 3-iodobenzaldehyde, 4-hydraxybenzaldehyde, 4-chtorobertzaldehyde, 4-bromobenzaldehyde, -fodobenzaldehyde, 2,4-dichlorobenzaldehyde, 2,4-dibromobenzaldehyde, 2,4-diiodobenzaldehyde, 2-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,4,6-trinitrobenzaldehyde, 2-formylbenzoic acid, 4-formylbenzoic acid, and terephthalaidehyde, furfural, acetone, butanone, dimethyl carbonate, diethyl carbonate, boric add, and boronic acids (R-B-(OH)2, where R is a C₁-C₆ alkyl, a C₅-C₈ cycloaliphatic group, or a phenyl group), ketoacids / ketoester (pyruvic acid, levulinic acid, oxaloacetic acid, 2-oxoglutaric acid), a hydroxymethylfurfural, (HMF, e.g, 5-hydroxymethylfurfura!, 5-HMF), 2-methoxyproane, 2,2-dimethoxypropane, and mixtures of such protecting reagents.

[0042]

[0024] An aldehyde donor, preferably a formaldehyde donor, may also be used as the protecting reagent. Formaldehyde donors include but are not limited to methylal, ethylal, glycerol formal, diformylxylose (DFX), Cyrene™ (Dihydrolevoglucosenone), diformyl glucose, diformyl pentaerythritol, polyvinyl acetals, pyvinyl butyrals, paraformaldehyde, hexamethylenetetramine, or mixtures thereof. A formaldehyde donor not only provides formaldehyde to protect the β-O-4 hydroxyl groups but can also act as the solvent for a solution or dispersion in a process of the invention. APatent Application Docket 24-41-FF01 single formaldehyde donor or mixture of formaldehyde donors or mixture of other protecting agents with formaldehyde donors may be used.

[0043] (02: A protecting reagent may be used "neat" or as a solution or dispersion of the protecting reagent. When a solution or dispersion of the protecting reagent, the solvent may be the same or different than the solvent used to form the biomass dispersion and preferably is the same as or miscible with that solvent. A protecting reagent is Combined with the iignocelluldsic material and solvent to form a biomass dispersion. Any order of addition may be used. Exemplary solutions of a protecting reagent which may be used include, but are not limited to, aqueous formaldehyde solutions, formaldehyde, diformylxylose (DFX) solutions, and formaldehyde levulinic acid solutions, where the protecting agent is present In 1-65 wt.%, or in 5-60 wt,%, 10-55 wt%, and 30-55 wt.%, far example, In same circumstances, the protecting agent itself may also be the solvent.

[0044]

[0026] The amount of solvent used to form a biomass dispersion should be sufficient to allow mixing of the lignoceilulosic material and the protecting reagent. Preferably, the amount of solvent should allow the biomass dispersion to be stirred or otherwise mixed during the reacting step. The amount of solvent in the biomass dispersion may be, for example, in the range of 1- to 20-times the amount of lignocellulosic material, on a weight-weight basis, in the biomass dispersion, or in the range of 1- to 10-times, or 5- to 15-times.

[0045]

[0027] The solvent may be, but is not limited to, water, an aqueous solvent containing one or more cosolvents or an organic solvent. While water is preferred, cosolvents may be added to solubilize or disperse components in the lignocellulosic material and / or the protecting reagent used in a process. A cosolvent may be added in any amount desired but is typically used in amounts up 50 wt.%.

[0046] Suitable cosolvents and / or organic solvents which may be used include but are not limited to 2-methyl THF, formaldehyde diethyl acetal (FDEA), THF, Diformyl xylose (DFX), 1,4-Dioxane, Dioxolane, Glycerol, glycerol formal, ketoacids / ketoester (levulinic acid, pyruvic acid, levulinic acid, oxaloacetic acid, 2-oxoglutaric acid), dimethylisosorbide, EDEA, acetone, cyclic ethers, cyclic carbonates, dialkyl carbonates, (e.g. dimethyl carbonate), a diaryl carbonate, cyclic esters, gamma valerolactone, non-cyclic ethers, methanol, ethanol, ethylal, ethers, nitriles, dimethoxyethane, toluene, dimethyl carbonate, diethyl carbonate, heptane, monoglyme, diglyme, carboxylic acids (formic), carboxamides, lactones, sulfoxides, maleic acid solution, 5-sulfosalylic acid solution, 1,4-epoxybutane, 4-methylbutyrolactone, formic acid butanol, acetic acid, butanone, and mixtures thereof.

[0047]

[0028] Additional hydroxy -functional additives known to react with formaldehyde may be added when preparing a biomass product or an adhesive composition of the invention. A hydroxy¬ functional additive may be present in a biomass product or a com position of the invention in anPatent Application Docket 24-41-FF01 amount ranging from 0.5 to 15 t, %, 5-12 wt %, or 7-10 wt. %< As is known in the art, hydroxy functional additives may be added for the purpose of scavenging protecting reagents, such as formaldehyde, which may reduce subsequent washing steps and reduce risk of emissions from the process. Their reaction products with protecting reagents may also enhance solubility of other adhesive additives when the protected lignocellulosic product is blended into adhesive compositions. Their reaction products With protecting reagents may also act as additional crosslfnkers or crosslinking donors in an adhesive system. One aspect of preparing a biomass product of the invention involves charging one or more hydroxy-functionalized additives, so that their reaction product with protecting reagents are above the solubility limit in the reaction vessel and subsequent washing steps. These hydroxy-functional additives Include but are not limited to: methanol, ethanol, isopropanol, pentaerythritol, xylose, fructose, ethylene glycol, sucrose, glucose, galactose, maltose, lactose, glycerol, polyvinyl alcohol (PVOH), sorbitol, mannitol, xylitol, maititol, lactitoi, isomait, erythritol, starches, other functionalized polyols, and mixtures thereof:

[0048]

[0029] Lignin in the lignocellulosic material in the biomass dispersion is reacted with the protecting reagent in the presence of a catalyst under reaction conditions to protect lignin -O-4 linkages in the lignocellulosic material to form a protected biomass dispersion. The reaction may be carried out at temperatures of S0-350X, more optimally from?0-275s'C, 80-220’C or 2(MJ-3D£FG The reaction may be acid or base catalyzed depending on the protecting group, as known to those skilled in the art. Suitable acid catalysts include, but are not limited to sulfuric acid, methanesulfonic acid, 2-ethenylbenzenesulfonic acid, p-toluenesulfonic acid (PTSA, such as PTSA monohydrate), hydrochloric acid, trifluoroacetic acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, phosphoric acid, hydrofluoric acid, formic acid, oxalic acid, terephthalic acid, lignosulfonic acid, zinc chloride, aluminum chloride, iron (ill) chloride, palladium chloride, boron trifluoride etherate, boron trifluoride, aluminum trifluoride, zirconium tetrachloride and silicon tetrabromide. Suitable base catalysts include, but are not limited to, metal hydroxides (sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide), metal oxides (magnesium oxide, calcium oxide, barium oxide), metal alkoxides (sodium methoxide, potassium methoxide), trlethylamine (TEA), pyridine, 1,3- Dia2abicydo(5.4.0]undec-7“er>e (DBU), lJ5-Diazabicycio[4.3.0)nan-5-ene (DBN), quinuclidine, morpholine, proline, 1,1,3 -Tetramsthyigua idioe TMG), and l,4’-diazobicycio[2,2.21ociane (DABCO). The catalyst content in the reaction mixture may be in the range of 1-50 wt.%, more optimally from 2-10 wt.%. The catalyst may be added as an aqueous solution, which may be the same solvent as used to make the dispersion. Typical reaction times range from 0.1-10 hours, more optimally 4-6 hours. The reaction may take place in a batch or continuous reactor such as a continuous flow or plug flow reaction.Patent Application Docket 24-41-FF01

[0030] After the reaction step, the protected biomass dispersion may be neutralized and, optionally, cooled or allowed to cool to room temperature. Neutralization of the reaction mixture may be done as appropriate as known in the art by adding a base, such as sodium hydroxide, or an acid, such as sulfuric acid. Alternatively, the protected biomass dispersion may be neutralized by distilling oft or washing out the acid or base catalyst. Washing can also be done to remove salts resulting from a neutralization step.

[0049]

[0031] In a process of the invention the reaction conditions may be chosen such that cellulose in the lignocellulosic material is hydrolyzed during the reaction, for example, by adding acid. This hydrolysis may take place during the reaction with the protecting reagent or in a subsequent step before or after the optional neutralization of the protected biomass dispersion.

[0050]

[0032] After the reaction step or the optional neutralization, all or a portion of the solvent is removed to yield a biomass containing protected lignocellulosic material. The solvent may be removed by means known in the art such as but not limited to vacuum drying, rotary evaporation, distillation, lyophilization, ambient or heated drying, phase separation, draining, filtration, and the like. Additional solvent may be added prior to the solvent removal to achieve better removal of the solvent used in the dispersion and / or excess protecting reagent or catalyst. When the solvent is removed by draining or filtration, the protected biomass product may be washed to remove entrained acid and / or solvent and further dried if desired. A washing step may serve to neutralize the protected biomass dispersion. Any filtrate and / or washings may be recycled for use in a subsequent process of the invention. The resulting protected biomass may be milled and / or sieved to a desired particle size. The solvent removal step and any subsequent washing: may also act to remove excess protecting reagent, for example formaldehyde, that is present in the protected biomass dispersion. The solvent may be recycled for reuse in subsequent processes of the: invention making a biomass product of the invention.

[0051]

[0033] The invention provides a biomass product containing protected lignocellulosic material prepared by a process of the invention and in the various embodiments described. For some protecting reagents, post-protection processing of the biomass may deprotect some or all of the β-O-4 or other hydroxyl functionality in the biomass without loss of its adhesive or other properties. Having undergone the protecting step, such biomass products are still considered "protected biomass" of the invention. As used herein, a "protected biomass", a "protected biomass dispersion", and a "biomass product containing protected lignoceliulosic material" refers to a biomass, a dispersion, or a lignoceliulosic materia! prepared: using a process of the invention which reacts a biomass dispersion with a protecting: reagent.Patent Application Docket 24-41-FF01

[0034] Compositions

[0052]

[0035] The invention provides a composition comprising, consisting essentially of, or Consisting of 5 to 70 wt.% of a biomass product containing protected lignocellulosic material, up to 90 wt.% of a solvent, and up to 30 wt.% of a catalyst or reactant for deprotecting, ring opening, or crosslinking with at least the protected β-O-4 linkages. A composition of the invention may be used to make a board or be part of a wood adhesive composition. One composition of the: invention is a wood adhesive comprising, consisting essentially of, or consisting of 5-70 wt.% of a biomass product containing protected lignocellulosic material; 0-90 wt.% solvent; and 1-30 wt.% of an acid catalyst, a base catalyst, an acetal deprotecting agent, or a ring opening reagent; and 0-50 wt.% additives. Reactants for crosslinking / curing include acids, bases, aldehyde donors, amines, isocyanates, and phenolic resins, as shown in the examples below.

[0053]

[0036] The solvent used in a composition of the invention may be the same as those listed above used to prepare the, biomass product or another known for wood adhesives. The amount of solvent desired may be achieved by only removing a portion of the solvent from the reaction. When a solvent such as 2-methyl-tetrahydrofuran, for example, is used to make the biomass product, it is generally desirable to remove all of the solvent. When water or an aqueous solvent is used, more solvent may be left in. Typical solvents for a composition of the invention, particularly a wood adhesive, include j but are not limited to, water, glycerol, glycerol formal, and propylene carbonate, gamma valerolactone, diformylxylose (DFX), levulinic acid, Cyrene'!4’ (Dihydrolevoglucosenone), dimethyl isosorhide, high boiling point carboxylic acids, esters, lactones, carbonates, ethers, ethyl acetate, ethanol, isopropanol, methanol. The solvent in the composition may be one or more of the formaldehyde donors discussed above, Preferred solvents for a composition of the Invention include water, polyvinyl alcohol, propylene carbonate, glycerin, or mixtures thereof. A solvent or mixture of solvents may be present in amounts of 5-80 wt,%, 20-70 wt.%, or 30-60 wt.%. When the solvent: is also an acetal donor, such as athylal, higher amounts may be used,

[0054]

[0037] A composition of the invention, such as a wood adhesive, may also contain a curable resin. A curable resin may be present in 0.5-15 wt. % of the composition or in amounts such as 1-10 wt.%, 2-7 wt. %, and 4-6 wt. %• Curable resins may function as co-binders or co-curatives with the protected biomass network, analogously to novolac systems shown in the examples. A curable resin includes but is not limited to a curable resin selected from the group consisting of formaldehyde-based resin, furfural-based resin, glyoxal-based resin, glyoxylic acid-based resin, propionaldehyde- based resin, isocyanate-based resin, epoxy-based resin, a cyclic acetai-based resin, or combinations thereof, in certain aspects, the curable resin is a novolac resin. A curable resin may be present in 0.5-15 wt. % of the composition or in amounts such as 1-10 wt.%, 2-7 wt- %, and 4-6 wt, %« In some aspects, thePatent Application Docket 24-41-FF01 curable resin is selected from the group consisting of diformylxylose (DFX)-novolac resin, diformyl glucose (DFG)-novolac resin, triformyi sorbitol (TFS)-novolac resin, diformylpentaerythritol (DFP)-novolac resin, and combinations thereof.

[0055]

[0038] As mentioned above, a composition such as a wood adhesive may be delivered or used in one or two parts. In a two-part system, one part contains the biomass product containing protected lignocellulosic material and another part contains the acid or base catalyst, an acetal deprotecting agent, or a ring opening reagent As mentioned, an acid catalyst, a base catalyst, an acetal deprotecting agent, or a ring opening reagent may be present in an amount of 1-30 wt.% of the adhesive composition, or in amounts for 2-20 wt. %, or 5-15 wt. %. Exemplary acid catalysts include, but are not limited to, para-toluenesulfonic acid (pTSA), methane sulfonic acid, sulfuric acid, 2-ethenylbenzenesulfonic acid, hydrochloric acid, trifluoroacetic acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, phosphoric acid, hydrofluoric acid, formic acid, lignosulfonic: acid. Zinc: chloride, aluminum chloride, iron (III) chloride, palladium chloride, boron trifluoride etherate, boron trifluoride, aluminum trifluoride, zirconium tetrachloride, and silicon tetrabromide. Suitable base catalysts include, but are not limited to, metal hydroxides (sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide), metal oxides (magnesium oxide, calcium oxide, barium oxide), metal alkoxides (sodium methoxide, potassium methoxide), triethylamine (TEA), pyridine, 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN), quinuclidine, morpholine, proline, i,i,3,3-Tetramethylguanidine (TMG), and 1,4- diazobicyclo[2.2.2]octane (DABCO), Exemplary acetal deprotecting agents and ring opening reagents include the acid and base catalysts just mentioned but also include, and are not limited to, water, methyl triflate, boron trifluoride etherate, 1,6-diaminohexane, ethylenediamine, thenyldiamine, trimethylhexamethylenediamine, and tripelennamine, polyethylenimine (PEI), and other reagents known in the art to ring open an acetal or a cyclic carbonate.

[0056] 1039] A wood adhesive of the invention may also contain additives known in the art for wood adhesives. When present, such additives may be present in an amount of up to 50 wt.%, or 0,1-20 wt.% or 0.5-15 wt.%, or 1-10 wt.%, of the wood adhesive. A wood adhesive may, for example, contain one or more additives including, but: not limited to a non-polar co-solvent, a polar co¬ solvent, a formaldehyde donor (e.g. diformyl xylose (DFX), CyreneTM, extracted formaldehyde-protected lignin (FPL), and the like), a defoamer, a viscosity modifier, a rheology modifier (such as polyvinyl alcohol, PVOH), a formaldehyde scavenger, a plasticizer, a filler, a flame retardant, a lubricant, a softening agent, a pigment, a biocide, a latent acid donor, a surfactant, a dispersant, a latex, a hydrophobic agent, a neutralizing agent (e.g., MgO, CaO), and a tackifier (e.g. a terpene phenolic resin). Such additives may be added in amounts known In the art, typically in individualPatent Application Docket 24-41-FF01 amounts of 0.01-20 wt.% or 0.5-10 wt.% of the wood adhesive- The adhesive may be heated after adding a formaldehyde scavenger to SO-IOO’C for 5-30 minutes to reduce the amount of free formaldehyde, A wood adhesive may also be a one component or a two-component system where one component contains the biomass product containing protected lignocellulosic material; and the other a component with accelerants or other additives for curing such as pMDI or cyclic acetal formaldehyde donors, epoxies, and the like,

[0057] [Q4D] A wood adhesive may be prepared using methods known in the art, for example, by making a paste, suspension, or solution, depending on the degree of solvating effects of the liquid components on the protected biomass. In the case of a paste application, the liquid component(s), such as water, would be added and then the protected biomass would be shear-mixed in, creating a paste. To form an emulsion, dispersing, bodying agents, surfactants, detergents, or thickener could be added to the liquid portion prior to biomass powder addition. In the case of a solution., the protected biomass would be dissolved in the solvent system, promoting Newtonian fluid behavior.

[0058]

[0041] A Wood adhesive of the invention is suitable for manufacturing a composite article and in particular, composite articles comprising substrates formed of lignocellulose material (i.e,, wood particles, wood fibers, straw, hemp, cotton stalk, wheat, bamboo, jute, flax, hard woods, soft woods, grasses, etc.), paper, fiberglass, eellufose, metal, sand, polymer materials, synthetic materials, and the like. Exemplary lignocellUlose-based composites include oriented strand board (OSB), particleboard, Hake board, medium or high-density fiberboard, Waferboard, plywood, laminated veneer layer (LVL), laminated glulam beam, mass timber, cross-laminated timber (CLT), medium density overlay (MDG), high density overlay ( HDO), an overlaid weather barrier, high pressure laminates (HPL), or thermally fused laminates (TFL), impregnated paper, paper board, and the like.

[0059]

[0042] A process for making a biomass product or composition, such as an adhesive composition, according to the invention may use reactors known in the art. For example, the biomass is treated in a filter bottom reactor, the solvent and excess protecting reagent is removed via filtration and washing, and the glue mix additives and solvents are subsequently added to the reactor, enabling the biomass treatment and adhesive formula to be made in a single reactor.

[0060]

[0043] Board and Composite Article Manufacture

[0061]

[0044] A process of making a board comprises the steps of forming the product biomass of the invention into a mat and pressing the mat at a pressure and temperature sufficient to form a board. The mat may be any desired shape, length or thickness depending upon the board to be manufactured. For example, the mat may be pressed into a rectangular shape with a thickness of, for example, i / 8", 1 / 4”, 3 / 8", 1 / 2", 5 / 8" or 3 / 4”, to manufacture a panel or shaped into a long rectangular shape dimensioned, for example, as a 2"xA” board or a l"x3" board., as such boards arePatent Application Docket 24-41-FF01 commonly used and referred to in the art. In a process of making a board according to the invention, a shaped mat may then be pressed with one or more plates at an elevated temperature sufficient to initiate curing and for a sufficient time to complete curing, forming the board,

[0062]

[0045] The invention also provides a process for manufacturing a composite article. In this process, wood adhesive is applied to at least one surface of a substrate to form a coated substrate, which is then pressed at an elevated temperature and for a time sufficient to cure the coated substrate and form the composite article

[0063]

[0046] A composite article, such as those discussed above, may be produced by applying an adhesive composition to a substrate, such as by coating, blending, spraying, or impregnating the substrate with the adhesive composition, forming a coated substrate such as those mentioned above. A wood adhesive may be applied to or blended with the substrate materials using any known method, such as by blender, roll coater, curtain coater, dip coater, spray booth, extruder, and the lite. The resulting composite may have 2 or more layers of adhesive composition.

[0064]

[0047] Processes for pressing a mat or pressing a coated substrate are generally carried out by hot pressing along with heat transfer from hot surfaces. As is known in the art, the temperatures and pressures vary depending upon the article being manufactured. The press pressure during which hot pressing occurs may be between 150 psi and 210 psi, including, for example, between 170 psi and 200 psi,, and between about 185 psi and 195 psi or at 190 psi. The temperature at which the mat or coated substrate is pressed may be at least 50”C for at least 2-25 minutes, such as a temperature of 100 °C to 325 °C or 150 °C to 300 °C for at least 2-25 minutes, a temperature of 100 " Cto 150 °C for at least 2-15 minutes, or, a temperature of 60 °C to 150 °C for at least 2-15 minutes including for example, 125 °C, for 2-20 minutes, 170 °C, for 10-15 minutes, or at 185 °C or 195 °C, for 5-15 minutes. Optionally, the farmed mat or composite article can be pre-pressed (e.g., cold pressed) prior to hot pressing. A composite article may be pre -pressed for a period of time, such as 1 minute to 60 minutes at ambient temperature prior to hot pressing, including, for example, a pre-pressing period of 1 minute to 20 minutes, or from 1 minute to 10 minutes. After the pressing step, the curing of a formed mat may be completed outside the press, such as by placing the pressed mat in an oven at an appropriate temperature (i.e., 100 °C-150 °C) to cure and form the board.

[0065]

[0048] Advantages and Technical Effect

[0066]

[0049] The processes and compositions of the invention provide several distinct advantages over previously known methods for producing lignin-based adhesives or composites. In conventional technologies, the lignin component of biomass is first chemically modified and then separated or extracted from cellulose and hemicellulose fractions prior to use. These extraction steps typically require large quantities of organic solvent, multiple filtration and washing stages, and energy¬Patent Application Docket 24-41-FF01 intensive drying. Each of these operations increases cost and complexity and can lead to significant loss of yield and deterioration of lignin reactivity through condensation or oxidation.

[0067]

[0050] In contrast, the invention performs the protective reaction within the intact I ignocellulosic matrix. The lignin, cellulose, and hemicellulose remain associated throughout the reaction and subsequent use. As a result, the β-O-4 linkages of lignin are protected from condensation, while the hydroxyl groups of the polysaccharide components participate in acetal or borate linkages with the protecting reagent. This creates a co-reactive network of stabilized lignin and carbohydrate components that, upon curing, forms an integrated adhesive matrix without the need for any lignin isolation or purification. The process is thus: one-pot and non-extractive, requiring no intermediate separation step.

[0068]

[0051] From a scientific standpoint, it would have been expected the presence of unremoved biomass constituents—such as cellulose, hemicellulose, extractives, proteins, and inorganic ash—to interfere with lignin modification and adhesive: performance. Conventional wisdom held that such materials dilute or deactivate lignin's reactive sites, impede β-O-4 protection, and disrupt curing reactions. Extraction-based lignin technologies were designed specifically to remove these interfering components and produce purified, reactive lignin fractions suitable for resin formulations.

[0069]

[0052] Unexpectedly, the inventors found that protecting lignin β-O-4 linkages in situ within the Whole biomass does not hinder performance but rather produces a stable and reactive adhesive material. The non-lignin fractions of the biomass proved to be beneficial, acting as physical scaffolds and co-reactants. Without being bound by theory it is believed that cellulose and hemicellulose participate in acetal or hydrogen-bonding interactions that retain lignin fragments in proximity and promote cohesive crosslinking during curing. The protective reagent can simultaneously link lignin and polysaccharide hydroxyl groups, yielding an interpenetrating network not achievable in systems based solely on extracted lignin.

[0070] [0531 The elimination of solvent-intensive extraction operations provides substantial manufacturing and environmental benefits. The reaction can be carried out using water or low- volatility solvents, producing minimal volatile organic compound (VOC} emissions. Energy consumption and solvent usage can be reduced by more than 50 % compared with extraction-based processes. Because the lignin remains within the biomass fibers, the resulting protected biomass product can be pressed or formulated directly into adhesives or boards, shortening process time and reducing waste.

[0071]

[0054] Surprisingly, these directly protected biomass products exhibit adhesive strength and durability equal to or greater than adhesives based on isolated protected lignin. Representative one- pot formulations achieved breaking loads of at least 150 psi and wood-failure percentages above 85Patent Application Docket 24-41-FF01 %, values comparable to or exceeding those obtained with extracted lignin adhesives. This level of performance, achieved in the presence of unremoved biomass constituents that would have been expected to be detrimental, demonstrates that the invention produces a non-obvious and technically superior result. The invention therefore provides a simpler, cleaner, and higher-performing route to renewable, biobased wood adhesives and composite boards,

[0072]

[0055] The terminology used here serves to explain not to limit the disclosure. Unless a specific context demands otherwise, singular terms should be read to include their plural forms and vice versa, and the articles "a," "an," and "the” are interchangeable with "at least one."

[0073]

[0056] The verbs '’'include" and "including" are intended to be open-ended in the same way "comprise” and 'comprising” are interpreted In patent claims. Likewise, the conjunction "or" should be understood as " A or B or both." unless the text expressly says, "only A or B, but not both."

[0074]

[0057] Unless the context states otherwise, any set of process steps described here can be carried out in any order

[0075]

[0058] All numerical values— amounts, temperatures, pressures, and so on— are to be taken as "about" those numbers. interpreted in light of significant digits and ordinary rounding, A stated range such as "1 to 10" covers every sub-range and individual value between 1 and 10, for example 1 to 6.1 or 2.3 to 9.4, as well as each integer from 1 through 10.

[0076]

[0059] Each expression of the invention described here (e.g,, method, composition, apparatus) may comprise, consist essentially of, or consist of the elements set out in this disclosure together with any optional features useful in an invention or In any preferred or derived embodiment,

[0077]

[0060] Embodiments of the Invention

[0078]

[0061] In the following, embodiments of the invention are described.

[0079]

[0062] In one embodiment, the invention relates to a process for making: a biomass product, comprising combining lignocellulosic material with a protecting reagent in a solvent to form a biomass dispersion, reacting lignin in the lignocellulosic material in the biomass dispersion with the protecting reagent in the presence of an acid catalyst or a base catalyst under reaction conditions sufficient to protect lignin β-O-4 linkages in the lignocellulosic material to form a protected biomass dispersion, optionally neutralizing the protected biomass dispersion, and removing all or a portion of the solvent from the protected biomass dispersion to yield a biomass product containing protected lignocellulosic material,

[0080]

[0063] In a further embodiment of the process, the solvent used to form the biomass dispersion is water or an aqueous solvent system.

[0081]

[0064] In a further embodiment of the process, the protecting reagent is selected from formaldehyde, ethylal, or boric acid.Patent Application Docket 24-41-FF01

[0065] In a further embodiment, the protecting reagent comprises formaldehyde or a formaldehyde donor capable of forming acetal-protected β-O-4 linkages in lignin.

[0082]

[0066] In a further embodiment, the invention relates to a biomass product obtainable by a process according to any of Embodiments 1–4, wherein the biomass product contains protected lignocellulosic material in which lignin β-O-4 linkages are protected against condensation.

[0083]

[0067] In another embodiment, the invention relates to a composition comprising 10 to 70 wt.% of a biomass product containing protected lignocellulosic material according to Embodiment 5, up to 90 wt.% of a solvent, and up to 30 wt.% of a catalyst or reactant for deprotecting, ring opening, or crosslinking with at least the protected β-O-4 linkages.

[0084]

[0068] In a further embodiment of the composition, the biomass product is selected from formaldehyde-protected biomass, ethylal-protected biomass, or boric acid-protected biomass.

[0085]

[0069] In a further embodiment of the composition, the solvent: is selected from water; polyvinyl alcohol, propylene carbonate, glycerin, or mixtures thereof

[0086]

[0070] In a further embodiment of the composition, the composition further comprises a formaldehyde donor,

[0087]

[0071] In a further embodiment of the composition, the composition further comprises a hydroxy-functional additive selected from methanol, ethanol, isopropanol, pentaerythritol, xylose, fructose, ethylene glycol, sucrose, glucose, galactose, maltose, lactose, glycerol, polyvinyl alcohol, sorbitol, mannitol, xylitol, maltitol, lactitol, isomalt, erythritol, starches, or mixtures thereof,

[0088]

[0072] In a further embodiment, the hydroxy-functional additive comprises fructose.

[0089]

[0073] In another embodiment, the invention provides a wood adhesive comprising 10 to 70 wt.% of a biomass product containing protected lignoceliulosic material, 0 to 90 wt.% solvent, and 1 to 30 wt.% of an acid catalyst, and optionally 0 to 50 wt.% of one or more additives.

[0090]

[0074] In a further embodiment of the wood adhesive, the biomass product is selected from formaldehyde-protected biomass, ethylal-protected biomass, or boric acid-protected biomass.

[0091]

[0075] In a further embodiment of the wood adhesive, the wood adhesive further comprises a hydroxy-functional additive, wherein the hydroxy-functional additive is fructose.

[0092]

[0076] In a further embodiment of the wood adhesive, the wood adhesive further comprises from 1 to 10 wt.% of a curable resin.

[0093]

[0077] In a further embodiment, the curable resin is a novolac resin.

[0094]

[0078] In a preferred embodiment, the invention provides a wood adhesive comprising a biomass product containing formaldehyde-protected or ethylal-protected lignocellulosic material, a solvent selected from water, glycerin, polyvinyl alcohol, propylene carbonate, or mixtures thereof, an acid catalyst, fructose as a hydroxy-functional additive, and a novolac resin as a curable resin.Patent Application Docket 24-41-FF01

[0079] Examples

[0095]

[0080] Example 1. Walnut Shell Flour Treatment

[0096]

[0081] 106,5 g of Walnut Shell flour (WF-7), purchased from The Willamete Valley Company, 946.6 g of 2-Methyl THF, 99.5 g of HCHO (53 wt.% in water), and 74,3 g of sulfuric acid (50 wt.% in water) were added to a reaction flask. The particle size of the WF-7 is 88 wt. % under 325 mesh and 100 wt. % Under 100 mesh. The contents were heated to 70,8 ’C for 4 hours, before cooling to room temperature. A mixture of 67.8 g of sodium bicarbonate in 70 g of deionized (DI) Water was added to the reaction flask to neutralize, while stirring, Flask contents were heated to 30 °C, under vacuum to distill off 2-Methyl THF. 368 g of water was charged to the reaction flask, after 40 min of distillation, to replace liquid content in flask, Distillation continued for another 50 min. The reaction flask contents were filtered through Whatman 3 filter paper and washed with 738.4 g of DI water. The wet biomass product powder containing protected lignocellulosic: material was lyophilized over night: to obtain 75.6 g of a dry, protected WF-7, powder product. Free water and formaldehyde content of treated biomass products are described in Table 39,

[0097]

[0082] Biomass samples were analyzed following the procedures reported in Yang, G. et. al Bonding wood with uncondensed lignins as adhesives, Nature, (2023). The biomass samples was partially solubilized in d6-DMSO, The sample was filtered with a 1.0 μm PTFE filter prior to analysis, to remove insoluble portions. An NMR spectrum was recorded on an Oxford 400 MHz spectrometer, HSQC characterizations were performed using the Bruker hsqcetgpsisp2.2 pulse sequence with the following parameters: acquired from 13 to 0 ppm in F2 (1H) with 2048 data points and a 2:s recycle delay. 200 to 0 ppm in F1 (13C) with 256 increments of 128 scans. The central DM50 solvent peak was used as the spectral reference. The peak observed at δH 4.7-5 ppm / δC 92-95 ppm is consistent with an acetal of formaldehyde protected β-O-4 linkage in lignin.

[0098]

[0099]

[0084] Wood adhesives, of Example 1 biomass product, were prepared per the formulations described in Table 1, All components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly, Plywood panels were pressed immediately fallowing glue application and assembly of plys- Finally, the plywood panels were cut Into three 1- inch sections and tested far wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 2, " FIT" indicates that the adhesive bond failed in testing, in other words it delaminated during vacuum pressure soaking.Patent Application Docket 24-41-FF01 Table 1. Example 2-5 Wood Adhesives

[0100] Component Example 2 Example 3 i Example 4 Example 5 | mass (gi mass lg) I mass (g) mass (g) J Example 1 Biomass 3 2.43 i 2.44 27.08 |

[0101] ................ „................ _ 1 Glycerin 0.1 i 0.11

[0102] 51 DFX

[0103] 70% pTSA monohydrate solution 1.12 1.02 | 1,02 10 Propylene Carbonate 3 0 | 0 9.01 § 11% PVOH Solution 1: 0.53 i Q.56 27.27 § Water 3 3 i 3,02 27.05 §

[0104]

[0105] Table 2. Example 2-5 Plywood Press Conditions and Performance

[0106] Example 2 I Example 3 Example 4 Example 5 Example 5 Panel 1 Panel 2...^.................... Adhesive application rate

[0107] per bond line (g)

[0108] -.. -.. - - - - Wood species Glued Poplar I Poplar Poplar Southern Douglas Fir Yellow Pine

[0109] Press T emperature i T) 299 i 299 299 266 266 Press Pressure (psi)

[0110] Press Time (minj 5 i 10 5

[0111] Wood Failure (%) gg

[0112] Breaking Load (psi) | 113 197 140 i 190 97 FIT 90

[0113]

[0114]

[0085] Example 6. Walnut Shell Flour Treatment

[0115]

[0086] 338 g of WF 7, 2880 g of 2-Me THF, 297 g of 53% aqueous formaldehyde solution, and 237,0 g of 96.6% sulfuric acid were combined in a reaction flask. The contents were heated to 74.4 " C for 4 hours. 1310 g of distillate were collected while cooling the reaction mixture to room temperature, 450g of water and 375 g of a 50% NaOH aqueous solution were charged to the reaction flask.1468 g of distillate was collected at 30" C, over 2 hours. During the distillation, 1056.9 g of water was charged to the reaction flask. Reaction contents were then filtered through a Whatman 3 filter paper and washed with 3242,86 g of Di water. The filter cake was lyophilized overnight, resulting in 247 g of biomass product.

[0116] [0871 Examples 7-8. Wood Adhesive Compositions and Plywood Panels

[0117]

[0088] Wood adhesives, of Example 6 biomass product, were prepared per the formulations described in Table 3. Ail components, excluding the 70% pT5A solution, were first mixed untilPatent Application Docket 24-41-FF01 thoroughly combined. Then the 7Q% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3 -ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. finally, the plywood panels were cut into three 1- inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard, The adhesive application rates, press conditions, and bond performance results are described in Table 4.

[0118] Table 3. Example 7-8 Wood Adhesives

[0119] Component j Example 7 Example 8

[0120] ! mass (g) mass (g) j Example 6 Biomass product 3 54

[0121] ................ _................

[0122] 70% pTSA monohydrate solution 1.12

[0123] Propylene Carbonate j 1 18

[0124] 11% PVOH Solution 3 54,02

[0125] Water | 3

[0126]

[0127] Table 4. Example 7-8 Plywood Press Conditions and Performance

[0128] Example 7 | Example 8 Panel 1 | Example 8 Panel 2 | Example 8 Panel 3 Adhesive application rate per bond line (g) 0.85 | 0.85 | 0.85 | 0.85 § | |

[0129] Wood Species Glued | Poplar | Southern Yellow Pine | Douglas Fir | PoplarPress Temperature (°F) | 266 j ~~~ ~~~ 268 i Press Pressure (psi) | 185 | 185 | 185 | 185 Press Time (min) | 5 j 5! 5 | 5 1 Wood Failure (%) ( 95 89 63 92 | Breaking Load (psi) | 113 197 | 137 | 108 | 128 | 166

[0130]

[0131]

[0089] Example 9. Walnut Shell Flour Treatment

[0132]

[0090] 130.8 g of WF-7, 1280.2 g of a 53% aqueous formaldehyde solution, and 95.7 g of a 50% sulfuric acid solution were combined in a reaction flask. The reaction contents were heated to 76.5°C, while stirring and held at temperature for 4 hours. The reaction flask was then cooled to room temperature 88,17 g of 50% NaOH solution and 44,44 g of DI water were charged to the flask to neutralize. The reaction contents were filtered through a Whatman 3 filter paper and washedPatent Application Docket 24-414401 With 960.4 g of DI water. 406 g <jf fl er cake was collected and lyophifeed overnight. 367 g c-f biomass product was obtained.

[0133]

[0091] Example 10. Wood Adhesive Composition

[0134]

[0092] Wood adhesive, of Example 9 biomass product, was prepared per the formulation described in Table 5. Ail components, excluding the 70% pTSA solution, were first mixed until thoroughly combined, Then the 70% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1-inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 6. ’’FIT" indicates that the adhesive bond failed In testing, in other words it delaminated during vacuum pressure soaking.

[0135] Table 5. Example 10 Wood Adhesive

[0136] Component I Example 10 mass (g)

[0137] Example 9 Biomass Product 5,44

[0138] Propylene Carbonate j 1,83

[0139] pTSA monohydrate solid | 2.12

[0140] 11% PVOH Solution | 5.44

[0141] Water j 5.40

[0142]

[0143] Table 6. Example 10 Plywood Press Conditions and Performance

[0144] | Example 10 Panel 1 Example 10 Panel 2 Adhesive application rate per bond line (g) 1 0.85 0.85

[0145] Wood Species Glued j Poplar Poplar Press Temperature (°F) | 266 266

[0146] Press Pressure (psi) | 185

[0147] Press Time (min) j 6 5

[0148] Wood Failure (%) | 7 FIT Breaking Load (psi) | 113 197 | 157 FIT

[0149]

[0150] [

[0151]

[0152]

[0093] Example 11. Walnut Shell Flour Treatment

[0153]

[0094] 329,3 g of WF -7, 799.7 g of a 53% Formaldehyde solution in water, 232.6 g of a 50% sulfuric acid solution, and 2287 g of water were combined In a reaction flask. Reaction contents were heatedPatent Application Docket 24-41-FF01 to 98.5®C, while stirring and held at temperature for 5 hours. The reaction flask was then cooled to room temperature, and the reaction contents were filtered through a Whatman 3 filter paper. The filtrate was collected for reuse, and the filter cake was then washed with 17,706.6 g of Di water. The filter cake was left to dry under ambient conditions for several days before washing again with 7654.3 g of DI water. The fitter cake was lyophilized, and 271.65 g of biomass product was collected.

[0154]

[0095] Example 12. Wood Adhesive Compositions and Plywood Panels

[0155]

[0096] Wood adhesive, of Example 11 biomass product, was prepared per the formulation described in Table 7, AU components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1- inch sections and tested fbr wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 8.

[0156] Table 7. Example 12 Wood Adhesives

[0157] i Component j Example 12 mass (g)

[0158] i Example 11 Biomass Product: j 4.1

[0159] I Glycerin | 2.01

[0160] pTSA monohydrate solid | 2.01

[0161] 11% PVOH Solution | 6.08

[0162] Water | 6.05

[0163]

[0164] Table 8. Example 12 Plywood Press Conditions and Performance

[0165] Example 12 i Example 12 Example 12 I Example 12 Panel 1 Panel 2 Pane! 3 Panel 4 Adhesive application rate per bond 1 1 line |g)

[0166] Wood Species Glued Poplar Poplar Poplar Poplar PressTemperature f F) 299 299 299 299

[0167]

[0168] i Press Pressure (psi) | 185 | 185 | 185 | 185 I Press Time (min) i 6 5. j.4. j 3 I Wood Failure (%) i 97 97 | 93 | 10 Breaking Load (psi) | 113 197 | 103 107 127 | 140

[0169]

[0170] Patent Application Docket 24-41-FF01

[0097] Example 13. Walnut Shell Flour Treatment

[0171]

[0098] 329.3 g of WF-7, 134.2 g of a 53% Formaldehyde solution in water, 42 g of a 50% sulfuric add solution, 379.2 g of DI water and 2769 g of recycled filtrate from Example 8 were combined in a reaction flask. The recycled filtrate contained 10.93% formaldehyde and 3.2% sulfate content.

[0172] Reaction contents were heated to 97,8°C, while stirring and held at temperature for 5 hours. The reaction flask Was then cooled io room temperature, and the reaction contents were filtered through a Whatman 3 filter paper: The filter cake was stirred with 1518 g of DI water and filtered again. This step was repeated with 1611 g of 01 water and then 1524 g of DI water. 274.75 g of wet filter cake was collected and dried in a desiccator under vacuum. 197.3 g of biomass product was collected.

[0173] [Q99] Example.14. Wood Adhesive Composition and Plywood Panels

[0174]

[0175]

[0100] Wood adhesive, of Example 13 biomass product, was prepared per the formulation described in Table 9. All components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 7Q% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3 -ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1- inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 10.

[0176] Table 9. Example 14 Wood Adhesive

[0177] Component Example 14 mass fg)

[0178] Example 13 Biomass Product j 20.4

[0179] Glycerin j 9.9

[0180] pTSA monohydrate solid | 10

[0181] 11% PVOH Solution 29.85

[0182]

[0183] Table 10. Example 14 Plywood Press Conditions and Performance

[0184] 1 Example 14 i Example 14 f Example 14 j Example 14 i Panel 1 j Panel 2 Panel 3 Panel 4 Adhesive application rate per bond i 1 1 1 | 1 | 1 Une {§) i ] 1

[0185] Wood Species Glued 1 Poplar i Poplar j Poplar | Poplar Press Temperature (’F) | 299 299 j 299 j 299

[0186]

[0187] Patent Application Docket 24-41-FF01

[0188] Pres.sTime imin) | 6 5 j 4 | 3 Wood Failure (%) | 95 j 92. j. 88. | 8 Breaking Load (psi) | 113 197 | 140 177 117 | 117

[0189]

[0190]

[0101] Example 15. Walnut Shell Flour Treatment

[0191]

[0102] 557,90 g of WF-7, 1670,7 g of a 53% Formaldehyde solution in water, 234,94 g of a 50% sulfuric acid solution, and 1239,9 g of DI water were combined in a reaction flask, Reaction contents Were heated to 98" C, while stirring and held at temperature for 5 hours. The reaction flask Was then cooled to room temperature, and the reaction contents were filtered through a Whatman 3 filter paper, The filter cake was stirred with 1505 g of Di water and filtered again, This step was repeated with 1512 g of DI water and then 1499 g of DI Water. 1206 g of wet filter cake Were collected and dried in a desiccator overnight. 683,4 g of biomass were collected from the desiccator and further lyophilized overnight. 379,8 g of biomass product was recovered.

[0192]

[0103] Example 16 – Wood Adhesive Composition and Plywood Panels

[0193] [1.04] Wood adhesive, of Example 15 biomass product, was prepared per the formulation described in Table 11. All components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1 • inch sections and tested for Wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 12.

[0194] Table 11, Example 16 Wood Adhesive

[0195]

[0196] Patent Application Docket 24-41-FF01 Table 12. Example 16 Plywood Press Conditions and Performance

[0197] | Example 16 Example 16 Example 16 Example 16 | Panel 1 Panel 2 Panel 3 Panel 4 Adhesive application rate per i 1.45 1.45 1.45 1.45 bond line (g) i

[0198] Wood Species Glued 1 Poplar Poplar Poplar Poplar Press Temperature CF) 1 299 299

[0199] Press Pressure (psi) | 185 185 185 185 Press Time (min) i 6 4 3 Wood Failure (%) | 95 95 95 75

[0200] ™...

[0201] Breaking Load (psi) | 113 197 | 113 137 133 213

[0202]

[0203]

[0105] Example 17, Walnut Shell Flour Treatment

[0204]

[0106] 330 g of WF-7, 1470.8 g of Ethylal, 232.9 g of a 50% sulfuric acid solution, and 1660 g of DI water were combined in a reaction flask. Reaction contents were heated to reflux (77.7°C), while stirring and held at temperature for 4 hours. The reaction flask was then cooled to room temperature, and the reaction contents were filtered through a Whatman 3 filter paper. 68.3 g of filter cake were taken for analysis, and the balance was stirred with 1506 g of DI water and filtered. The filter cake was then stirred with 1516 g of DI water and filtered again. The filter cake was lyophilized for 2 days. 247.75 g of biomass product was collected.

[0205]

[0107] Example 18. Wood Adhesive Composition and Plywood Panels

[0206] Wood adhesive, of Example 17 biomass product, was prepared per the formulation described in Table 13, All components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3-piy plywood assembly. Plywood panels were pressed immediately foliowing glue application and assembly of plys. Finally, the plywood panels were cut into three l-inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 14,

[0207] Table 13, Example 18 Wood Adhesive

[0208]

[0209] Patent Application Docket 24-41-FF01

[0210]

[0211] Table 14. Example 18 Plywood Press Conditions and Performance

[0212] I i Example 18 | Example IS | Example 18 Example 18 i i Panel 1 Panel 2 Panel 3 Panel 4 Adhesive application rate per 0,85 0,85 0.85 0.85 bond line (g) >

[0213] Wood Species Glued Poplar j Poplar Poplar Poplar Press Temperature (T) 299 299 299 299 Press Pressure (psi) 185 185 185 185 Press Time (min) | 6 5 4 3 Wood Failure (%) | 97 90 17 15 Breaking Load (psi) | 113 197 127 103 150 147

[0214]

[0215]

[0108] Example 19. Walnut Shell Flour Treatment

[0216]

[0109] 612.86 g of WF-7, 2373,9 g of Ethylai, and 215.33 g of 96.6% Sulfuric Acid were charged to a reaction flask. Reaction contents were heated to 80°C while stirring and held at temperature for 5 hours. The reaction flask was then cooled to room temperature and neutralized with 359.64 g of a 50% aqueous NaOH solution. The reaction contents were then filtered through a Whatman 3 filter paper and washed with 2 L of water. The filter cake was lyophilized and the resulting biomass product was recovered,

[0217]

[0110] Example 20. Wood Adhesive and Plywood Panels

[0218]

[0111] Wood adhesive, of Example 19 biomass product, was prepared per the formulation described in Table 15. All components, excluding the 70% pTSA solution. were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1- inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard, The adhesive application rates, press conditions, and bond performance results are described in Table 16.Patent Application Docket 24-41-FF01

[0112] Table 15. Example 20 Wood Adhesive

[0219] Component | Example 20 wt. %

[0220] Example 19 Biomass Product | 20.38

[0221] Glycerin 9.91

[0222] pTSA monohydrate solid 9.99

[0223] 11% PVOH Solution 29.85

[0224] Water 29.96

[0225]

[0226] Table 16. Example 20 Plywood Press Conditions and Performance

[0227] Example 20 Example 20

[0228] Panel 1 Panel 2

[0229] Adhesive application rate per 0.85 0.85

[0230] bond line (g)

[0231] Wood Species Glued Douglas Fir Douglas Fir

[0232] Press Temperature (°F) | 302

[0233] Press Pressure (psi) | 185 185

[0234] Press Time (min) 5 3

[0235] Wood Failure (%) 13 85

[0236] ........................

[0237] Breaking Load (psi) | 113 197

[0238]

[0239]

[0113] Example 21. Walnut Shell Flour Treatment

[0240]

[0114] 154.57 g of WF-7, 838.92 g of Ethylal, and 53.79 g of 96.6% Sulfuric Acid were charged to a reaction flask. Reaction contents were heated to 80’C while stirring and held at temperature for 5 hours. The reaction flask was then cooled to room temperature and neutralized with 89.6 g of a 50% aqueous NaOH solution. The reaction contents were then filtered through a Whatman 3 filter paper and washed with 1L of water. The filter cake was lyophilized, and 132,75 g of biomass product was recovered.

[0241]

[0115] Example 22. Wood Adhesive Composition and Plywood Panels

[0242] Wood adhesive, of Example 21 biomass product, was prepared per the formulation described in Table 17. All components, excluding the 70% pTSA solution and Dead-Burned Magnesium Oxide (MgO) P98-30, purchased from Martin Marietta Magnesia Specialties, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute. Finally the MgO was added and stirred until evenly dispersed, immediately prior to gluing on a 3 in x 3 in, 3 -ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1-inch sections and tested far wetPatent Application Docket 24-41-FF01 shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 18,

[0243] Table 17. Example 22 Wood Adhesive

[0244] Component Example 22 wt.

[0245] %

[0246] Example 21 Biomass Product 30

[0247] Glycerin j 10 j

[0248] 70% pTSA monohydrate solution | 10 |

[0249] 11% PVOH Solution | 40 |

[0250] Dead-Burned MgO P98-30 | 0.7

[0251] Water j 9.3

[0252]

[0253] Table 18. Example 22 Plywood Press Conditions and Performance

[0254] i 1 Example 22 Example 22 | Example 22 Example 22 | | Panel 1 Panel 2 | Panel 3 Panel 4 | Adhesive application rate per I 0.85 0.85 0.85 0,85 i bond line [g| i

[0255] i Wood Species Glued 1 Douglas Fir Douglas Fir i Douglas Fir Douglas Fir ~~~ _

[0256] | Press Temperature (°F) | 266 266 266 257 i Press Pressure (psi] I 185 185 | 185 185

[0257] .............. ~............... |.............. ~............... „............... | Press Time (min) | 3 5 7 5

[0258] ........................... |...........................

[0259] | Wood Failure (%) | 92 97 93 92

[0260] i Breaking Load (psi) | 113 197 100 127 | 110 i 173

[0261]

[0262]

[0116] Example 23. Walnut Shell Flour Treatment

[0263]

[0117] 350.80 g of 53% formaldehyde, 551.67 g of denatured ethanol, and 53.76 g of 96.6% Sulfuric Acid were charged to a reaction flask. Reaction Contents were heated to 80”C while stirring and held at temperature for 3 hours. 156,23 g of WF-7 was added to the reaction mixture while holding temperature for an additional 5 hours. The reaction flask was cooled to room temperature, and reaction contents were filtered through a Whatman 3 filter paper. The filter cake was stirred with 2L of water and re-filtered. The filter cake was lyophilized, and 136.01 g of biomass product was recovered.Patent Application Docket 24-41-FF01

[0118] Example 24. Wood Adhesive Composition and Plywood Panels

[0264]

[0119] Wood adhesive, of Example 23 biomass product, was prepared per the formulation described in Table IS. All components, excluding the 70% pTSA solution and Dead-Burned MgO P98-30, purchased from Martin Marietta Magnesia Specialties, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute. Finally the MgO was added and stirred until evenly dispersed, immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1 -inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 20,

[0265] Table 19. Example 24 Wood Adhesive

[0266] Component | Example 24 wt.

[0267] %

[0268] Example 23 Biomass Product j 30

[0269] Glycerin j 10

[0270] 70% pTSA monohydrate solution | 10

[0271] 11% PVOH Solution 40

[0272] Dead-Burned MgO P98-30 1 0.7

[0273] Water t 9.3

[0274]

[0275] Table 20. Example 24 Plywood Press Conditions and Performance

[0276] Example 24 Example 24 Example 24 Example 24 Panel 1 Panel 2 Panel 3 Panel 4 Adhesive application rate per 0.85 0.85 0.85 bond line ig)

[0277] Wood Species Glued Dougl as Fi r Douglas Fir Douglas Fir Douglas Fir Press Temperature (°F) | 266 266 266 257

[0278] Press Pressure (psi) | 185 185 185 185 Press Time (min) 3 5 7 5

[0279] “g

[0280] Wood Failure (%) | 65 88 50 95

[0281] Breaking Load (psi) | 113 197 120 157 143 157

[0282]

[0283] Patent Application Docket 24-41-FF01

[0120] Example 25. Walnut Shell Flour Treatment

[0284]

[0121] 84.87 g of WF-7, 1198.55 g of water, 81.18 g of boric acid, and 136.05 g of a 50% NaOH aqueous solution were added to a reaction flask. The flask was heated to 80 *C while stirring and held at temperature for 5 hours. Then, the reaction vessel was cooled to 30 “C, 141.8 g of a 37% aqueous hydrochloric acid solution was charged to the flask to neutralize to a pH of 6.4 over 1 hour. Reaction contents were then filtered over a Whatman 3 filter paper, and the filter cake was washed with 800 g of DI water. The filter cake was lyophilized and 62.80 g of biomass product was collected,

[0122] Example 26. Wood Adhesive Composition and Plywood Panels

[0285]

[0123] Wood adhesive, of Example 25 bidmass product, Was prepared per the formulation described in Table 21. All components, excluding the 50% pTSA solution, were first mixed until thoroughly combined. Then the 50% pTSA solution was added and mixed for 1 minute. The adhesive was applied to 3 in x 3 in veneers and stacked in a 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys, Finally, the plywood panels were cut into three 1-inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 22.

[0286] Table 21. Example 26 Wood Adhesive

[0287] Component | Example 26 wt.

[0288] _ j %

[0289] Example 25 Biomass Product j 20.38

[0290] Glycerin j 9.91

[0291] 50% pTSA monohydrate solution | 19.98

[0292] 11% PVOH Solution j 39.85

[0293] Water _ [ 19,88

[0294]

[0295] Table 22. Example 26 Plywood Press Conditions and Performance

[0296] Example 26 Example 26 Example 26 Example 26 Example 26 Example 26 Panel 1 Panel 2 Panel 3 Panel 4 Panel 5 Panel 6 Adhesive 0.85 0,85 0,85 0,85 0,85 0,85 application rate

[0297] per bond line (g)

[0298] Wood Species Poplar Poplar Poplar Douglas Fir Douglas Fir Douglas Fir Glued

[0299] Press 302 302 302 302 302 302 Temperature fFJ

[0300] Press Pressure 190 190 190 190 190 190

[0301]

[0302] (psi)Patent Application Ducket 24-41-FF01 Press Time (min) ] 3

[0303] Wood Failure (%i § 20 88 95 27 17 85 Breaking Load 183 80 80 93 | 90: iso

[0304]

[0305] (psi) | J in

[0306]

[0124] Examp e 27. Wood Adhesive Composition and Plywood Panels

[0307]

[0125] Wood adhesive, of Example 25 biomass product, was prepared per the following formulation. 22.6 wt% of Exampie 25 biomass product was mixed with 69,9% water and 7.5% of a 50% aOH in water solution. These components were mixed at room temperature for 1 minute. The adhesive was applied at a rate of 0.85 g per bondline to 3 in x 3 in veneers and stacked in a 3-ply plywood assembly. A plywood pane! Was pressed at 150 ®C and 190 psi immediately following glue application and assembly of plys. The resulting panel showed good adhesion. The individual veneers could not be separated by hand.

[0308]

[0126] Example 28. Walrn.!: Sheil Fiour Treatment

[0309]

[0310]

[0127] 135,25 g of WF-7, 378.70 g of Dimethyl Carbonate, 782.66 g of 2-Me THF, 75.38 g of water, and 151.33 g of a 50% NaOH aqueous solution were added to a reaction flask. The flask was heated to reflux (68.4°C) white stirring and held at temperature for 4 hours. Then, 125.2 g of distillate was collected over 30 min, and the reaction vessel was cooled to room temperature, 185.2 g of a 50% Aqueous Sulfuric Acid solution Was charged to the flask to neutralize over 1 hour. The flask as then heated to 30C, while pulling full vacuum to distill, 429,5 g of distillate were collected. 470g of Di was charged to the flask, before continuing to distill an additional 357g, SOO g of water was charged to the flask. Reaction contents were then filtered over a Whatman 3 filter paper, and the filter cake Was washed with 11.187.6 g of □> water. The filter cake was lyophilized and 126 g of biomass: product was collected,

[0311]

[0128] Examples 2930. WoodAdhesives and Py wood Panes

[0312]

[0129] Wood adhesive, of Example 28 biomass product, was prepared per the formulations described in Table 23. All components, excluding the 60% polyethyleneimine solution [PEI], were first mixed until thoroughly combined. Then, the 60% polyethyleneimine solution (PEI) solution was added and mixed fo i minute, Immediately prior to gluing on a 3 In x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1 -inch sections anti tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 24.Patent Application Docket 24-41-FF01 Table 23. Examples 29-30 Wood Adhesive

[0313] Component Example 29 wt. % Example 30 wt. % Example 28 Biomass Product 29.92 31.26

[0314]

[0315] Table 24. Examples 29-30 Plywood Press Conditions and Performance

[0316] I Example 29 Example 30 Example 30 | Panel 1 Panel 1 Panel 2 Adhesive application rat® per 1 1.45 1.4S bond line (g[ _

[0317] Wood Species Glued Southern Teltow Southern Yellow Southern Yellow Pine Pine Pine Press Temperature (:F) j 302 302 302 Press Pressure [psi] | 185 185 185 J’ressJImefmin) _ j 10

[0318] Wood Failure (%) | 2

[0319] Breaking Load (psi) | 113 197 j 67 30 73

[0320]

[0321]

[0130] Example 31, Walnut Shell Flour Treatment

[0322]

[0131] 330.60 g of Walnut Shell flour { WF-5), purchased from The Willamette Valley Company, 806.5 g of Formaldehyde (53 wt.% in water], 232.87 g of sulfuric acid (50 wt.% in water),, and 2298.15 g of water were added to a reaction flask. The particle size of the WF-5 is 88 wt. % under 200 mesh and 100 wt. % under 50 mesh. The contents were heated to reflux (97.6) ’C for S hours, before cooling to room temperature. 219.48 g of hlaOH (50% in water] was added to the reaction flask to neutralize, While shr rmg The reaction flask contents were filtered through Watman 3 filter paper and washed three times with 2000 g of water each. The wet biomass product powder containing protected lignocelluloslc material was lyophilized overnight to obtain 200.09 g of a dry, protected WF-5, powder product.Patent Application Docket 24-41-FF01 1132] Examples 32-33, Wood Adhesive and Plywood Panels

[0323]

[0133] Wood adhesives, of Example 31 biomass product, were prepared per the formulations described in Table 25, All components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute. For Example 32 Panels 1-3 [Pl-3} and Example 33 Panel 1 (Pl), the adhesive was immediately applied on a 3 in x 3 in, 3-ply plywood assembly. For Example 32 Panels 4-7 (P4-7), the adhesive was aged for 12 days after the acid addition prior to gluing onto 3 in x 3 in, 3-piy plywood assemblies. Plywood panels were pressed immediately following glue application and assembly of plys, Finally, the plywood panels were cut Into three l-irsch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 26.

[0324] Table 25, Example 32-33 Wood Adhesives

[0325] Component Example 32 mass (g) Example 33 mass (g)

[0326] Example 31 Biomass 30.9 4.14

[0327] Glycerin 14.9 2.01

[0328] pTSA monohydrate 15.26 2.03

[0329] 11% PVOH Solution •44.8 6.06

[0330] Water 44,8 6.07

[0331]

[0332] Table 28, Example 32 -33 Plywood Press Conditions and Performance

[0333] Example Example Example Example Example Example Example Example 33 – P1 32 – P1 32 – P2 33 – P1 32 – P4 32 – P5 32 – P6 32 – P7 Adhesive 0,85 0.85 0,85 0,85 0,85 0.85 0.85 0,85 application rate

[0334] per bond line (g)

[0335] Wood Species Poplar Poplar Poplar Poplar Poplar Poplar Poplar Poplar Glued

[0336] Press 302 302 302 257 302 302 302 266 Temperature (°F)

[0337] Press Pressure 185 IBS 185 185 185 185 185 185 (psi)

[0338] Press Time (mln) 5 4 3 5 5: 4 3 5 Wood Failure (%i 95 98 7 83 97 100 9S 87 Breaking Load 157 150 190 223 150 123 97 130

[0339]

[0340] _

[0341] U34j Comparative Example 1, Poplar Furnish Treatment

[0342]

[0135] Poplar veneer was ground and sieved to a particle size of 0.841 mm, 153 grams of poplar veneer, 1300 grams of 1^4-dioxane, 130 grams of formaldehyde solution (53 wt.% in water), 11 gramsPatent Application Docket 24-41-FF01 of ^ater, and 52 grams of hydrochloric acid solution (37 wt.% in water) were added to a reaction flask. The flask contents were heated to 80 “C, while stirring and reacted for 5 hours before cooling to room emperature. The biomass contents were filtered and washed with 800 grams of 1,4- dioxane. A mixture containing 56.23 grams of sodium bicarbonate and 669 grams of water was added to the hitrate to neutralize. Then, 4000 grams of water were added to the filtrate to precipitate the extracted lignin. The precipitated lignin Was filtered, and the collected solids were lyophilized to obtain 34 grams of product.

[0343] 1136] Exa rnpfe^34^P plarf jur jsh Treatrng nt

[0344]

[0137] Poplar veneer Was ground and sieved to a particle size of 0*075 - 0,21 mm. Moisture content of the resulting poplar powder was 5.62%. 1Q6 grams of the poplar powder, 901 grams of 2 -Methyl TH!7, 105 grams of formaldehyde solution (53 wt.% in water), and 38 grams of sulfuric acid solution (97 wt.% in water) were added to a reaction flask. The reaction was carried out with continuous stir ring over 4 hours at 73'C.80 grams of sodium bicarbonate, dispersed in 84 grams of water, was added to the reaction mixture, While stirring and cooling to ambient temperature. 355 grams of 2- Methyl THF was used to wash lignocellulqsle material from the edges of the flask into the reaction mixture. The 2-Methyi THF was then distilled under vacuum at ambient temperature. 66 grants of propylene carbonate and 600 grams of water were charged to the reaction flask. Water was removed via rotary evaporation at 50-55 *C. The biomass product containing protected lignocellulosic material Was rinsed with an additional 233 grams of DI Water, followed by rotary evaporation to remove excess formaldehyde. 235 g of a powder product was obtained.

[0345] Example 35. Wood Adhesive and Plywood Panels

[0346]

[0138] 7.6 grams of powder product from Example 34 was added to 2.25 grams of propylene carbonate, 2 grams of deionized (DI) Water, and 1.38 grams of p-toiuenesulfonic acid monohydrate solutson (70 wt.% in water). The mixture was stirred for one minute and then applied to 3 in:< 3 in poplar plywood veneers. About 1 gram of wood adhesive mixture was applied to each bond line. The plywood panel was pressed at 190 psi and 239 ’F for 10 min to produce a 3-ply poplar plywood board. While the resulting panel consolidated, the strength was poor and the bonds could be pul ted apart by hand.

[0347]

[0139] Example 36, Poplar Furnish Treatment

[0348]

[0140] 295 g of protected poplar biomass product from Example 34 was washed with 868.7 g of DI water over a Whatman 3 filter to remove salts from neutralization. The washed filter cake was lyophilized and 61.2 g of washed, protected biomass product was recovered.

[0349]

[0141] Biomass samples were analyzed following the procedures reported in Yong, &. et Al Banding wodrf with uncondensetf lignins as adhesives, Alotere, (2023}. The biomass samples was partiallyPatent Application Docket 24-41-FF01 solubilized in d6-DMSO, The sample wasfiltered with a 1,0 gm PTFE filter prior to analysis, to remove insoluble portions. An NMR spectrum was recorded on an Oxford 400 MHz spectrometer. H5QC characterizations were performed using the Broker hsqcetgpsisp2.2 pulse sequence with the following parameters; acquired from: 13 to 0 ppm in F2 (1H| with 2048 data points and a 2s recycle delay. 200 to 0 ppm in F1 (13C) with 256 increments of 128 scans. The central DMSO solvent peak Was used as the spectral reference. The peak observed at 5H 4.7-5 ppm / SC 92-95 ppm is consistent with an acetal of formaldehyde-protected β-O-4 linkage in lignin.

[0350]

[0142] Exam pies 37-38, W od Adhesive and PI wqpd Pane is

[0351]

[0143] Wood adhesives, of Example 36 biomass product, were prepared per the formulations described in Table 27. All components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute. The adhesive was immediately applied onto 3 in x 3 in, ply plywood assemblies, Ply wood panels were pressed immediately following glue application and assembly of plys, Finally, the plywood panels were cut into three 1-inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 28.

[0352] Table 27. Examples 37-38 Wood Adhesive

[0353] Component Example 37 Mass (g) Example 38 Mass (g) Example 36 Biomass 3.04 2.49

[0354] Glycerin 0 0.13

[0355] DFX 0 3.09

[0356] pTSA monohydrate (70% in water! 1.14 1.03

[0357] Propylene Carbonate 1.04 0

[0358] 11% PVOH Solution 3,03 0.54

[0359] Water 3.03 3.03

[0360]

[0361] Table 28. Examples 37-38 Plywood Press Conditions and Performance

[0362] Example 37 Example 38 Example 38 Panel 1 Panel 1 Panel 2 Adhesive application rate per bond line (g) 0.85 0.85 0.85 Wood Species Glued Poplar Poplar Poplar Press Temperature (" F) 302 302 302

[0363] Press Pressure (psi) 185 185 185

[0364] 5

[0365]

[0366] Press Time (min) 10 5Patent Application Docket 24-41-FF01

[0367]

[0368] Breaking Load (psi) | 113 197

[0369] [144 ) Example 39, Poplar Treatment

[0370]

[0145] Poplar veneer was milled to a particle size of <20 mesh. 153.2 g of the milled poplar veneer, 145.1 g of a 53% aqueous formaldehyde solution, 52.2 g of 37% aqueous hydrochloric acid solution, and 718.4 g of Levulinic Acid were charged to a reaction flask. The contents were heated to 8Q’C while stirring and held at temperature for 5 hours and 45 min. The reaction was then cooled to room temperature, and the reaction contents were filtered over a Whatman 3 filter paper. The filter cake Was washed with 9325.6 g of DI water. The filter cake Was lyophilized and 134.04 g of biomass product was collected,

[0371] [146) 6xampje4Q-41. WoodAdhesive and Plywood Panels

[0372]

[0373]

[0147] Wood adhesive, of Example 39 biomass product, was prepared per the formulation described in Table 29. All components, excluding the pTSA, were first mixed until thoroughly combined. Then the pTSA was then added and mixed for 1 minute, immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys, Finally the plywood panels were cut into three 1-inch sections and tested for breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1- 22 standard. The adhesive application rate:-:-, press conditions, and bond performance results are described in Table 30,

[0374] Table 29. Examples 40-41 Wood Adhesive

[0375] Component j Example 40 wt. % Example 41 wt. % Example 39 Biomass Product 20.1

[0376] Propylene Carbonate j 9.0 10.3 pTSA monohydrate _ j 5.0 6,6 11% PVOH Solution | 27.1 20.8

[0377] DI Water j 38,8 41.6

[0378]

[0379] Patent Application Docket 24-41-FF01 Table 30. Examples 40-41 Plywood Press Conditions and Performance

[0380] Example 40 Example 40 Example 41 Example 41 Example 41 Panel 1 Panel 2 Panel 1 Panel 2 Panel 3 Adhesive application rate i 0,85 0.85 i! 1 1 j per bond line (g) i

[0381] Wood Species Glued 1 Douglas Fir Douglas Fir Douglas Fir i Douglas Fir Douglas Fir j Press Temperature (°F) | 257 257 302 | 302 302 | Press Pressure (psi) 1 190 190 190 |.190 190 j Press Time (min) i 4 5 6 j Wood Failure (%) | 20 37 32 | 25 85 |

[0382] ____ ___ __ ____ Breaking Load (psi) | 113 197 i 137

[0383]

[0384]

[0148] Example 42, SYPTreatment

[0385]

[0149] 152.0 g of Southern Yellow Pine [SYP), ground to <20 mesh (large particle size), 132.5 g of Formaldehyde (53% aq. Solution), 84 g of Sulfuric Acid (96.6% aq. Solution), 676.30 g of water, and 304,2 g of MeOH were charged to a reaction flask. The contents were heated to 80°C while stirring and held at temperature for 5 hours before cooling to room temperature. The reaction flask was heated to 55°C and 310 g of distillate were collected over 25 min. The reaction contents were cooled to room temperature and washed With 2154 g of water and filtered over Whatman 3 filter paper.

[0386] The protected biomass filter cake was then lyophilized, and 122.65 g of protected lignocellulosic product was collected.

[0387]

[0150] Example 43. Wood Adhesive and Plywood Panels

[0388]

[0151] Wood adhesive, of Example 42 biomass product, was prepared per the formulation described in Table 31, All components, excluding the pTSA and Dead-Burned MgO P9S-30, were first mixed until thoroughly combined. Then the pTSA was then added and mixed for 1 minute, and then the MgO was mixed quickly until evenly dispersed and immediately prior to gluing on a 3 in x 3 in, 3- ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1 -inc h sections and tested for breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 32.Patent Application Docket 24-41-FF01

[0389] Table 31. Example 43 Wood Adhesive

[0390] i Component Example 43 wt. %

[0391] i Example 42 Biomass Product 19,87

[0392] i Propylene Carbonate 4.99

[0393] pTSA monohydrate 6.95

[0394] i Glycerin 10.3

[0395] i Fructose 10.13

[0396] Dead-Burned MgO P98-30 0.59

[0397] i 11% PVOH Solution 20

[0398]

[0399] i Di Water 27,17

[0400] Table 32. Example 43 Plywood Press Conditions and Performance

[0401] Example 43 Example 43 Example 43 Example 43

[0402] Pane! 1 Panel 2 Panel 3 Panel 4 Adhesive application rate 1.36 1.36 1.36 1.36

[0403] per bond line (g)

[0404] Wood Species Glued Douglas Fir Douglas Fir Douglas Fir Douglas Fir

[0405] Press Temperature (°F) 302 302 302 302

[0406] Press Pressure (psi) 190 190 190 190

[0407] Press Time (min) 4 5 6 7

[0408] Wood Failure (%) 0 0 0 0

[0409]

[0410] Breaking Load (psi) | 113 197 0 □ 8 0

[0411] (152) Example 44. Southern Yeliow Pine Treatment

[0412] (153) Southern Yeliow Pine (5YP) veneers were ground to a particle size of less than 200 mesh (reduced particle size). 68,35 g of ground SYP, 160.27 g of Formaldehyde (53% aq. Solution), 47.8 g: of Sulfuric Acid (50% aq. Solution), and 484.65 g of Water were added to a reaction flask- The reaction contents were heated to reflux (97.5’C) while stirring and held at temperature for 5 hours before cooling to room temperature. The reaction contents were filtered through a Whatman 3 filter paper. The filter cake was mixed with 300 g of DI water and filtered again. This step was repeated twice more with 400 g of water and then with 406 g of water. The product was dried in a desiccator under vacuum and 48 g of protected lignocellulose product was obtained.

[0413] (154) Examples 45-45. Wood Adhesive and Plywood Panels

[0414] (155) Wood adhesive, of Example 44 biomass product, was prepared per the formulation described in Table 33. Ail components, excluding the 70% pTSA solution, were first mixed until thoroughly combined. Then the 70% pTSA solution was added and mixed for 1 minute immediatelyPatent Application Docket 24-41-FF01 prior to gluing on a 3 in x 3 m, 3 -ply plywood 'assembly Plywood panels were pressed immediately fellowing glue application and assembly of pl v Finally, the plywood panels were cut into three 1 • inch sections and tested for wet shear breaking strength and percent wood failure following vacuum pressure soaks, per the PS 1-22 standard. The adhesive application rates, press conditions, and bond performance results are described in Table 34,

[0415] Table 33. Examples 45-46 Wood Adhesive

[0416] I Component | Example 45 wt. % | Example 46 wt, % i Example 44 Biomass Product | 17.18 | 15.93 Glycerin | 9.63 | 7.94

[0417] i pTSA monohydrate solid j 11.1 1 6.69

[0418] i 11% PVOH Solution 25.69 | 18.27 Propylene Carbonate 0 4.61

[0419] i Fructose | 0 | 9,72

[0420] i Water | 36,4 36.84

[0421]

[0422] Table: 34. Examples 45-46 Plywood Press Conditions and Performance

[0423] Example 45 Example 45 Example 45 Example 45 Example 46 Panel 1 Panel 2 Panel 3 Panel 4 Panel 1 Adhesive application rate 1.45 i 1.45 1.45 J 1.45 0.85 | per bond line (g)

[0424] Wood Species Glued Poplar i Poplar I Poplar j Poplar Poplar 1 Press Temperature (°F) 266

[0425] - - j Press Pressure (psi) 185 Press Time (min) 6 5 4 3 5 Wood Failure (%)

[0426] Breaking Load (psi) | 113 197 113 [ 150 2Qg 163 |

[0427]

[0428]

[0156] Example 47. SYP, WF-5, and Xylose Combined Treatment

[0429]

[0157] 10,5 g of SY ground ta <200 mesh, 10,6 g of WF-5, 112.8 g of formaldehyde (53% aq.), 8.24 g of sulfuric acid (96.6% aq.), 89.08 g of Water, and 24.13 g of xylose were charged to a reaction flask. The contents were heated to reflux (93.9”C) while stirring and held at temperature for 4 hours. The temperature was decreased to 75“C and 91,71 g of Denatured Ethanol was charged to the reaction flask. The reaction was held at 75" C for one hour before distilling off ethanol and the reaction products of ethanol and formaldehyde. The reaction flask was cooled over an ice bath and thenPatent Application Docket 24-41-FF01 contents were, filtered through a Whatman 3 filter paper. The filter cake was rinsed with 24 g of cold water before lyophilising, 21.3g of protected biomass product were obtained.

[0430] J 158] Exampie 48. G utngs

[0431]

[0159] Wood adhesive, of Exampie 47 biomass product, was prepared per the formulation described in Table 35. All components, excluding the 70S» pTSA solution, were first mixed until thoroughly combined. Then the 7Q% pTSA solution Was added and mixed for 1 minute immediately prior to gluing on a 3 in x 3 in, 3-ply plywood assembly. Plywood panels were pressed immediately following glue application and assembly of plys. Finally, the plywood panels were cut into three 1- inch sections and tested for wet shear breaking strength and percent wood failure foliowing vacuum pressure soaks, per the PS 1*22 standard, The adhesive application rates, press conditions, and bond performance results are described in Table 36,

[0432] Tabid 35. Exarnple 48 Wood Adhesive

[0433] I Component j Example 48 wt, % LExampie47 Biomass Prcduct 20,87

[0434] Plenco 15847 Novolac |

[0435] i PPG 425 _ j 1,42

[0436] I pTSA monohydrate solid j 8.93

[0437] I Propylene Carbonate | 0.99

[0438]

[0439]

[0440] Table 36. Example 58 Plywood Press Conditions and Performance

[0441] i Example 48 Example 48 Example 48 Example 48 i Panel 1 Panel 2 Panel 3 Panel 4 Adhesive application rate per i 1.45 1.45 1.45 1.45 bond line (g) i

[0442] Wood Species Glued i Poplar Poplar Poplar Poplar Press Temperature (°F) | 302 302 302 302 Press Pressure (psi) \ 185 185 185 185 Press Time [min] i 7 5 4 3 Wood Failure (%) 90 85 85 92

[0443]

[0444] Patent Application Docket 24-41-FF01

[0445]

[0446]

[0160] Example 49, Walnut Shell Floor Treatment

[0447]

[0161] 153.8 g of WF-7, 882.7 g of Ethyial, 54.21 g of a 96.6% sulfuric acid solution, were combined in a reaction flask, Reaction contents were heated to reflux (80°C), while stirring and held at temperature for 5 hours. The reaction flask was then cooled to room temperature, and the reaction contents were filtered through a Whatman 3 filter paper. The filter cake was then stirred with 1L of DI water and filtered again. The filter cake was lyophilized and 113.5 g of biomass product Was collected.

[0448]

[0162] Example 50. Fiberboard panel

[0449]

[0163] Protected walnut shell flour product (WSF, 105 g), from Example 49, was mixed with para-toluene sulfonic acid (10.5 g, 70% aq. solution), polyvinyl alcohol (9.5 g, 11% aq. solution), and water (15 g]. The sample was loaded into a 6" *4" x 2.75" (l,w,h) stainless steel mold and pre-pressed with a fitted cover at 100 psi for 1 minute. The mold was then removed, leaving a compacted or densified brictette, which was sandwiched between two 7" x 5® stainless steel plates and placed into a hydraulic press with electrically heated platen (EHP) set to 350°F. The brickette was then compressed to a thickness of 0.4", controlled by the use of two stainless steel stopper rods. The sample was left to cure over the course of 5 minutes, after which the pressure was released, and the sample was left to cool to ambient temperature. The resulting fiber panel was machinable and sawed to and even rectangular shape. As shown in Table 37, protected biomass products consistently exhibit low free formaldehyde levels, supporting reduced emissions during adhesive curing. The level of free formaldehyde in these adhesives can be further reduced, if desired, by additional water washing or with the inclusion of a formaldehyde scavenger during the biomass treatment. (NA = not available.)

[0450] Table 37. Treated Lignocellulosic Biomass Residuals

[0451] [ Example _ ] W a ter Co n t e nt (%) i F ree H CH O ( % )

[0452] i 1 16.55 1 0.1854

[0453] ] 6 [ 10.84 | 0.2172

[0454] i 9 [ 7.23 [ 2.91

[0455] [ 11 fsS i 0,0164

[0456] UlZZZZZZZlf^^

[0457] I 15 [ 2.13 [ 6.9007

[0458] fl? ' 18.81} f 04403

[0459] [ 19 [iZll [ 0.0036

[0460] Hl f'3^82 [ 04)179

[0461] [ 23 [ 1.83 ] 0.046

[0462] fz5 p_

[0463] p

[0464]

[0465] 28 pili FNAPatent Application Docket 24-41-FF01 i 31 i 0.2505

[0466] i 34 [1.5050

[0467] p36 Hli8S4

[0468] [42

[0469] pS

[0470] [47

[0471] [

[0472]

[0473] 49

Claims

Patent Application Docket 24-41-FF01 The claimed invention is:

1. A process for making a biomass product comprising the steps of:combining lignocellulosic material with a protecting reagent in a solvent to form a biomass dispersion,reacting lignin in the lignocellulosic material in the biomass dispersion with a protecting reagent in the presence of an acid catalyst or a base catalyst under reaction conditions to protect lignin β-O-4 linkages in the lignocellulosic material to form a protected biomass dispersion, optionally neutralizing the protected biomass dispersion, andremoving all or a portion of the solvent from the protected biomass dispersion to yield a biomass product containing protected lignocellulosic material.

2. A process of claim 1, wherein the reaction conditions are sufficient to also hydrolyze lignocellulosic material in the biomass dispersion.

3. A process of claim 2, further comprising, prior to or during the reaction step, the step of sonicating the biomass dispersion to break down the lignocellulosic material.

4. A process of any one of claims 1-3, wherein at least a portion of the solvent is removed from the protected biomass.

5. A process of any one of claims 1-3, wherein the solvent is removed from the protected biomass.

6. A process of any one of claims 1-5, further comprising, prior to the solvent removal step, the step of mixing the protected biomass with an additional solvent.

7. A process of any one of claims 1-6, wherein the solvent is water.

8. A process of any one of claims 1-7, wherein the protecting reagent is selected from the group of an aldehyde, an aldehyde donor, a ketone, a carbonate, boric acid and a boronic acid.

9. A process of claim 8, wherein the protecting reagent is selected from formaldehyde, ethylal, or boric acid.Patent Application Docket 24-41-FF01 10. A process of claim 9, wherein the protecting reagent is formaldehyde or a formaldehyde donor11. A process of any one of claims 1-10, wherein the reacting step comprises adding a catalyst to the biomass dispersion and heating to a temperature where the protecting reagent reacts with the lignin β-O-4 linkages in the lignocellulosic material.

12. A process of any one of claims 1-11, wherein the process includes the step of neutralizing the protected biomass.

13. A biomass product prepared by a process of any one of claims 1-12.

14. A composition comprising:10 to 70 wt.% of a biomass product of claim 13,up to 90 wt.% solvent, andup to 30 wt.% of a catalyst or reactant for deprotecting, ring opening, or crosslinking with at least the protected β-O-4 linkages.

15. A composition of claim 14, wherein the biomass product is selected from formaldedyde-protected biomass, ethylal-proctected biomass, or boric acid-protected biomass.

16. A composition of any one of claim 14 or 15, wherein the solvent is selected from water, polyvinyl alcohol, propylene carbonate, glycerin, or mixtures thereof.

17. A composition of any one of claims 14-16, further comprising a formaldehyde donor.

18. A composition of any one of claims 14-17, further comprising a hydroxy-functional additive selected from the group consisting of methanol, ethanol, isopropanol, pentaerythritol, xylose, fructose, ethylene glycol, sucrose, glucose, galactose, maltose, lactose, glycerol, polyvinyl alcohol (PVOH), sorbitol, mannitol, xylitol, maltitol, lactitol, isomalt, erythritol, starches, and mixtures thereof.

19. A composition of claim 18, wherein the hydroxy-functional additive is fructose.Patent Application Docket 24-41-FF01 20. A process of making a board comprising the steps of:forming a biomass product of claim 13 into a mat, andpressing the mat at a pressure and temperature sufficient to form a board.

21. A board made by a process of claim 20.

22. A wood adhesive comprising 10-70 wt.% of a biomass product containing protected lignocellulosic material, 0-90 wt.% solvent, and 1-30 wt.% of an acid or base catalyst, and optionally 0-50 wt.% additives.

23. A wood adhesive of claim 22, comprising 5-80 wt. % solvent, and 5-15 wt. percent of an acid catalyst.

24. A wood adhesive of claim 22 or 23, wherein the biomass product is selected from formaldedyde-protected biomass, ethylal-proctected biomass, or boric acid-protected biomass.

25. A wood adhesive of any one of claims 22-24, wherein the solvent is selected from water, polyvinyl alcohol, propylene carbonate, glycerin, or mixtures thereof.

26. A wood adhesive of any one of claims 22-25, further comprising a formaldehyde donor.

27. A wood adhesive of claim 26, further comprising a hydroxy-functional additive selected from the group consisting of methanol, ethanol, isopropanol, pentaerythritol, xylose, fructose, ethylene glycol, sucrose, glucose, galactose, maltose, lactose, glycerol, polyvinyl alcohol (PVOH), sorbitol, mannitol, xylitol, maltitol, lactitol, isomalt, erythritol, starches, and mixtures thereof.

28. A wood adhesive of claim 27, wherein the hydroxy-functional additive is fructose.

29. A wood adhesive of any one of claims 22-27, further comprising 1-10 wt. % of a curable resin.

30. A wood adhesive of claim 29, wherein the curable resin is selected from the group consisting of formaldehyde-based resin, furfural-based resin, glyoxal-based resin, glyoxylic acid-based resin,Patent Application Docket 24-41-FF01 propionaldehyde-based resin, isocyanate-based resin, epoxy-based resin, a cyclic acetal-based resin, or combinations thereof.

31. A wood adhesive of claim 29, wherein, the curable resin is a novolac resin.

32. A wood adhesive of any one of claims 22-31, comprising 0.1-20 wt.% of an additive.

33. A wood adhesive of claim 32, wherein the additive is selected from a neutralizing agent, a tackifier, and combinations thereof.

34. A process for manufacturing a composite article comprising the steps of:applying a wood adhesive of any one of claims 22-33 to at least one surface of a substrate to form a coated substrate andpressing the substrate at an elevated temperature and for a time sufficient to cure the coated substrate and form the composite article.

35. A process of claim 34, wherein the composite article is plywood, a laminated veneer layer (LVL) product, laminated glulam beam, mass timber, oriented strand board (OSB), cross-laminated timber (CLT), particle board, medium density fiberboard (MDF), impregnated paper, or paper board.

36. A process of making an adhesive composition in a single reactor, comprising the steps of: preparing a biomass product according to a process of any one of claims 1-12 in w in a filter bottom reactor,removing at least a portion of the solvent and excess protecting reagent via filtration and washing in the filter bottom reactor, andoptionally adding at least one of a hydroxy-functional additive, a curable resin, a solvent or an additive to the filter bottom reactor.

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