High-strength adhesives from sustainable components

Abstract

A high-strength adhesive composition comprising components such as (i) an epoxidized oil, (ii) a nucleophile, and (iii) a phenolic compound derived from sustainably sourced, low-cost biological materials available on a large scale: its use; and a method of manufacturing.

Description

HIGH-STRENGTH ADHESIVES FROM SUSTAINABLE COMPONENTSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is related to U.S. provisional patent application no. 63 / 338,465 filed May 5, 2022, and International Patent Application No. PCT / US23 / 66649 filed May 5, 2023. The contents of each of the aforementioned patent applications are hereby incorporated by reference in their entirities.STATEMENT OF GOVERNMENT SUPPORT

[0002] This invention was made with government support under N00014-19-1-2342 awarded by the Office of Naval Research. The government has certain rights in the invention.TECHNICAL FIELD

[0003] The present disclosure relates to high-strength adhesives manufactured using sustainable components. In particular, the disclosure relates to high-strength adhesives comprising bio-based materials, which enhance recycling and enable a sustainable materials ecosystem.BACKGROUND

[0004] This section introduces aspects that may help facilitate a better understanding of the disclosure. Accordingly, these statements are to be read in this light and are not to be understood as admissions about what is or is not prior art.

[0005] Most consumer products, from electronics to furniture, are held together with adhesives. High performance, versatility, and low cost are characteristics of modem glues. However, such traits also give rise to several environmental drawbacks. These materials are derived from petroleum, which creates permanent bonds, lacks chemical degradation, and is toxic. Due to this non-natural sourcing of adhesives, most components cannot be separated for recycling. An inability to degrade bonds disallows substrate separation, prevents recycling, and forces products to landfills. These discarded adhesive resins further contribute to the problem of ocean microplastics. Toxicity can also be a concern with, for example, the binders in plywood emitting carcinogenic formaldehyde. Society is awash in single-use products and packaging.

[0006] Biomimetic chemistry, inspired by the adhesives of shellfish, provides the required crosslinking. Biologically sourced adhesives may provide a needed path toward a sustainable materials ecosystem. In this regard, adhesives inspired from sea-creatures like mussels, barnacles, and oysters have been researched as a source of adhesives. These sea-creatures can adhere tightly to surfaces underwater, while withstanding not only a wet and changing sea environment, but also turbulent waves. Further, such marine life can remain adhered to rocks for years at a time. Thesecharacteristics have inspired researchers to develop tissue adhesives and sealants that mimic their adhesion chemi stry.

[0007] The attachment system of sea mussels is called “byssus” which is secreted from the foot of the mussel and consists of several threads terminating in an adhesive plaque. The byssus is composed of roughly 25-30 different proteins out of which only 7-8 are present in the plaque and only 5 (Mytilus foot protein type 2 (mfp-2), Mytilus foot protein type 3 (mfp-3), Mytilus foot protein ty pe 4 (mfp-4), Mytilus foot protein type 5 (mfp-5) and Mytilus foot protein type 6 (mfp- 6)) are unique to the plaque. One of the key components in sea mussel adhesive is a molecule called 1-3,4-dihydroxyphenylalanine (DOPA), which is largely found in mfp-3 and mfp-5.

[0008] Mussel-inspired adhesives have been synthesized using a variety of strategies. Natural polysaccharides like chitin, cellulose, hyaluronic acid, chitosan, silk fibroin, and the like have been modified with 3,4-dihydroxy-L-phenylalanine (L-DOPA), hydro caffeic acid, dopamine by surface chemistry’ and covalent conjugate to develop mussel-inspired, polysaccharide-based tissue adhesives. The polymer chain backbone of synthetic polymers has also been modified using dopamine or L-DOPA. Synthetic polymers like polystyrene, polylactic acid, and polyethylene glycol have been tuned to incorporate DOPA chemistry. Moreover, DOPA groups have been incorporated into recombinant protein systems via lysine and tyrosine incorporation. However, these conventional mussel-inspired adhesives can be costly and difficult to synthesize, require curing additives and other components, exhibit poor adhesivity, and can exhibit toxicity issues.

[0009] Thus, there is an unmet need for a high-strength adhesive that can be easily recycled, safe for the ecosystem, low-cost, manufactured using bio-based materials, and readily available on a large scale. It is an object of the present disclosure to provide such an adhesive. This and other objects and advantages, as well as inventive features, will be apparent from the detailed description provided herein.SUMMARY

[0010] Provided is an adhesive composition comprising (i) an epoxidized oil (EO). (ii) at least one nucleophile, and (iii) at least one phenolic compound.

[0011] The epoxidized oil can be any suitable epoxidized oil. In certain embodiments, the epoxidized oil is obtained from a sustainable source. In some embodiments, the sustainable source can be a plant or a vegetable. In some embodiments, the epoxidized oil is epoxidized soy oil.

[0012] The at least one nucleophile is any suitable nucleophile that is sufficiently nucleophilic to open an epoxy’ ring on the epoxidized oil when mixed therewith. In certain embodiments, the nucleophile is bio-based. In certain embodiments, the nucleophile is a multifunctional nucleophile. In certain embodiments, the nucleophile comprises at least two functional groups to facilitatecrosslinking reactions with the epoxidized oil. The at least one nucleophile can comprise two or more different nucleophiles.

[0013] The at least one nucleophile can be a compound comprising a moiety selected from the group consisting of an acid, an alcohol, an amine, and a thiol. In some embodiments, the nucleophile can be selected from fumaric acid, glycerol, malic acid, succinic acid, or a combination thereof. In some embodiments, the nucleophile is malic acid.

[0014] The adhesive composition can comprise one or more different phenolic compounds. The phenolic compound has a chemical structure that comprises ahydroxyl-substituted aromatic ring. The aromatic ring can be substituted with one or more hydroxyl groups. In certain embodiments, a phenolic compound comprises ahydroxyl-substituted aryl group. A phenolic compound can also include polyphenol, which can have more than one hydroxyl-substituted aromatic rings (e.g. , wi th one or more hydroxyl groups attached to the more than one aromatic rings). In certain embodiments, the phenolic compound comprises at least two hydroxyl groups. In certain embodiments, the phenolic compound comprises at least three hydroxyl groups. In certain embodiments, the phenolic compound comprises 2 or 3 hydroxyl groups.

[0015] The phenolic compound can be selected from catechol, gallic acid, gallol, lignin, tannic acid, or a combination thereof. In some embodiments, the phenolic compound is tannic acid.

[0016] In some embodiments, the adhesive composition can optionally further comprise a solvent. The solvent can be aqueous and / or organic. Examples of the solvent include, but are not limited to, alcohol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide. In some embodiments, the solvent can be alcohol, such as ethanol or methanol.

[0017] In some embodiments, the EO, at least one nucleophile, and at least one phenolic compound can be present in a mass ratio from about 1:0. 1:0.1 to about 1 : 10: 10, respectively.

[0018] In some embodiments, an adhesive composition consisting essentially of (i) epoxidized soy oil (ESO), (ii) malic acid, (iii) tannic acid, and (iv) ethanol. The ESO, malic acid, and tannic acid are present in a mass ratio from about 1:0.1:0.1 to about 1 : 10: 10, respectively.

[0019] Adhered substrates are also provided. In certain embodiments, an adhered substrate comprise a substrate comprising any of the adhesive compositions hereof applied thereto. The substrate can be exposed to dry. wet, moist, or underwater conditions. The substrate can comprmise metal, wood, plastic, ceramic, or any combination thereof. The metal substrate can be steel or aluminum. In certain embodiments, when cured on the substrate, the adhesive composition chemically bonds and / or adheres to the substrate.

[0020] Provided is a method of manufacturing the adhesive composition hereof, which method comprises: mixing a phenolic compound with an epoxidized oil to obtain an EO solution or mixture, wherein the phenolic compound is optionally in the form of a solution in a solvent; addinga nucleophile to the EO solution or mixture and heating said EO solution or mixture; and cooling the EO solution or mixture to room temperature, whereupon the adhesive composition is obtained.

[0021] The EO can be epoxidized soy oil. In certain embodiments, further comprising heating the EO prior to mixing the phenolic compound therewith. In certain embodiments, the EO and EO solution or mixture are both heated or maintained at a temperature of about 70° C to about 90 °C (e.g., to obtain the desired viscosity). The EO solution or mixture can be heated at a temperature of about 70° C to about 90 °C. The EO solution or mixture can be heated overnight and cooled to room temperature to obtain the adhesive composition.

[0022] The solvent can be selected from alcohol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide. The nucleophile can be a compound comprising a moiety selected from the group consisting of an acid, an alcohol, an amine, and a thiol. The nucleophile can be selected from fumaric acid, glycerol, malic acid, succinic acid, or can be a combination thereof. In certain embodiments, the nucleophile is malic acid. The phenolic acid can be selected from catechol, galhc acid, gallol, lignin, tannic acid, or a combination thereof. The phenolic compound can be tannic acid.

[0023] The adhesive composition can be used to adhere substrates. The substrates can be exposed to dry, wet, moist, or underwater conditions. The substrates can be selected from metal substrates such as steel or aluminum, wood, plastic such as polyvinyl chloride (PVC) or polytetrafluoroethylene (Teflon), ceramic, or a combination thereof. In some embodiments, the metal substrate can be steel or aluminum.

[0024] Provided is a method of using the adhesive composition, which method comprises applying the adhesive composition to at least a first substrate, which is to be adhered to at least a second substrate, and adhering the first substrate and the second substrate to each other such that the adhesive composition is sandwiched therebetween. The method can further comprise applying the adhesive composition to the second substrate prior to adhering the first substrate and the second substrate. At least one of the substrates can be (or have been) exposed to dry, moist, wet, or underwater conditions. In certain embodiments, the first substrate and / or the second substrate comprise a metal, wood, plastic, ceramic, or any combination thereof. In certain embodiments, the metal is steel or aluminum.BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The present disclosure will be more readily understood from the detailed description of embodiments presented below , considered in conjunction with the attached drawings of which:

[0026] Fig. 1 shows an adhesion as a function of varied ratios between the components epoxidized soy oil, glycerol, and tannic acid (soy-gly-tan). The substrates were untreated aluminum and cured at 180 °C for 24 hours.

[0027] Fig. 2 shows an adhesion as a function of varied ratios between the components epoxidized soy oil, malic acid, and tannic acid (soy-mal-tan). The substrates were untreated aluminum and cured at 180 °C for 24 hours.

[0028] Fig. 3 shows the adhesion of soy-mal-tan over time when cured at 180 °C and with polished steel substrates.

[0029] Fig. 4A shows the adhesion values for soy-mal-tan when compared against commercial adhesives with polished steel substrates.

[0030] Fig. 4B shows the adhesion values for soy-mal-tan when compared against commercial adhesives with sandblasted aluminum substrates.

[0031] Fig. 5 shows the adhesion values for soy-mal-tan when compared against commercial adhesives with polyvinyl chlonde (PVC) substrates. The bar for Super Glue shows the force at which the PVC substrates broke.

[0032] Fig. 6 shows the adhesion performance of a sustainably sourced adhesive. A) illustrates the lap shear bonding of soy-mal-tan with sandblasted steel, B) illustrates the lap shear bonding of soy-mal-tan with polished aluminum, C) illustrates the lap shear bonding of soy-mal-tan with teflon, and D) illustrates lap shear bonding of soy-mal-tan with pine wood substrates. In each case, comparisons are made to commercial glues, which were cured according to instructions from the manufacturers. Bonds with soy-mal-tan and metal substrates were cured for 6 hours at 180 °C, whereas teflon substrates used a 24-hour cure, also at 180 °C. Curing for wood bonding was at 120 °C for three days. Panel E) shows how the use of soy-mal-tan caused the failure of the wood substrates prior to the breaking of the adhesive bond.

[0033] Fig. 7 shows scanning electron microscopy (SEM) images of adhesives after being pulled to failure. A commercial epoxy shows clean fracture and distinct regions of adhesive versus substrate. The soy-mal-tan material shows more complex failure, with stress lines, indicative of ductile behavior. Both substrates were polished steel. The soy-mal-tan adhesive was cured at 180 °C for 6 hours.

[0034] Fig. 8 shows the appearance of the soy-mal-tan system at different stages. A) Epoxidized soy oil, malic acid, and tannic acid upon initial mixing at room temperature. B) Soy- mal-tan after 24-hour reaction time at 70 °C. The adhesive precursor was maintained at 70 °C and viscous but flowing. C) After the 24-hour reaction at 70 °C, cooling to room temperature brought about an increase in viscosity . D) Hardening after a 24-hour cure at 180 °C and scraped off substrates.

[0035] Fig. 9 shows the characterization of soy-mal-tan. A) illustrates ’H NMR spectra in DMSO-riri of the components, combinations, and the final formulation. B) illustrates13C NMR spectra in DMSO-t / 6 of malic acid, selected reaction products, and soy-mal-tan. Diethyl malate is provided for an ester reference. C) illustrates infrared spectra of the carbonyl (C=O) region. D) illustrates infrared spectra of the acid (CO-OH) region.

[0036] Fig. 10 A) shows the water resistance of soy-mal-tan to artificial sea water. Bonded pairs of polished aluminum substrates, with 1.2 x 1.2 cm overlap area, were cured in the air for 24 hours at 70 °C or 6 hours at 180 °C and then submerged underwater for varied periods of time. The x-axis is a log plot in minutes, labeled in hours for clarity. B) shows a pickup truck rocker panel with pieces of steel bonded together using rivets (top) and soy-mal-tan adhesive (bottom). Each assembly is held up by a string (beige) on the top. A 15-pound weight is hanging from the bottom.

[0037] Fig. 11 shows testing the resistance of soy-mal-tan adhesion to boiling water. The substrates used were polished aluminum.DETAILED DESCRIPTION

[0038] For the purposes of promoting an understanding of the principles of the present disclosure, reference will now be made to the embodiments illustrated in the drawings, and specific language will be used to describe the same. No limitation of scope is intended by the description of these embodiments. On the contrary, this disclosure is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of this application as defined by the appended claims.

[0039] Epoxy glues can be formed by the reaction of multifunctional epoxy-containing compounds, such as bisphenol A diglycidyl ether, with polyamines, including tri ethylenetetramine. Nucleophilic amines can open the three-membered epoxy rings and generate C-N bonds to form extensively cross-linked matrices. Soy oil, one of the most widely available sources of renewable organics, is an alternative to epoxies. A simple reaction of soy oil with acid and hydrogen peroxide can yield epoxidized soy oil. It is a low-cost bio-based material that is readily available at large scales. But epoxidized soy oil on reaction with polyamines yields only viscous oils, which are not good for adhesion and hence can not be a straight-up replacement for bisphenol A diglycidyl ether.

[0040] A key component in sea mussel attachment systems is a molecule called 1-3,4- dihydroxy phenylalanine (DOPA). DOPA groups enable proteins to bond to surfaces via hydrogen bonds and metal chelation, amongst several other interactions. Furthermore, oxidation of these pendant dihydroxyphenyl ( / .e., catechol) groups can facilitate cross-linking to provide cohesiveinteractions. Thus, when catechol-like chemistry is included in the adhesive formulations, epoxidized soy oil can be transformed into strong adhesives.

[0041] In view of the above, the present disclosure provides an adhesive composition comprising (i) an epoxidized oil (EO), (ii) a nucleophile (e.g., one or more nucleophiles), and (iii) a phenolic compound (e.g.. one or more phenolic compounds). In certain embodiments, the adhesive composition consists essentially of, or consists only of, an EO, a nucleophile, and a phenolic compound.

[0042] The adhesive composition can be a high-strength adhesive comprising components derived from a sustainable biological source. The biological source can be an agricultural feedstock that is low-cost, readily available on a large scale, and easily recycled. In certain embodiments, one or more of the components of the adhesive composition can be derived from a sustainable biological source.

[0043] The epoxidized oil can be a natural oil (e.g., an oil derived from an animal or a plant). The epoxidized oil can be any suitable EO obtained from a sustainable source. The sustainable source can be a plant. The sustainable source can be a vegetable (e.g., a vegetable oil). Suitable nonlimiting examples of oils that can be epoxidized include oils that have two or more non-conjugated carbon-carbon double bonds. In certain embodiments, the oil that can be epoxidized is avocado oil. canola oil, palm oil, Brazil nut oil, citrus seed oil, com oil, cocoa butter, cottonseed oil, linseed oil, oat oil, peanut oil, olive oil, rapeseed oil, safflower oil, sesame oil, soybean oil, sunflower oil, or any combination of two or more of the foregoing oils.

[0044] Epoxidized oil can be derived from an animal or plant and reacted with an epoxidizing agent to form epoxy groups at sites of carbon-carbon double bonds (i.e., whether natural or synthetic); however, the epoxidized oil is not limited to formation by such means. Non-limiting examples of epoxidizing agents include a peracid, a perester, and / or a peroxide. In certain embodiments, the epoxidized oil can be a naturally occurring expoidized oil such as Vernonia oil.

[0045] The epoxidized oil can have numerous epoxy groups but is not limited to a certain number of epoxy groups per molecule, so long as the epoxidized oil includes at least one epoxy group. In certain embodiments, the epoxidized oil has two, three, four, or five internal epoxy groups. In certain embodiments, the epoxidized oil can have more than five internal (or terminal) epoxy groups. In certain embodiments, the epoxidized oil can have six, seven, eight, nine, ten, or more than ten epoxy groups. In certain embodiments, the epoxidized oil can be approximately one hundred percent (100%) expoxidized.

[0046] In certain embodiments, the epoxidized oil has a viscosity of from about 300 to about 700 cps at 25 °C (such as about 300 to 700, 300 to about 700, or 300-700 cps at 25 °C), about 400 to about 600 cps at 25 °C (such as about 400 to 600, 400 to about 600, or 400-600 cps at 25 °C), orabout 600 cps at 25 °C, wherein the stated ranges are inclusive of the stated end points and all 1 increments contained therein. Nevertheless, the epoxidized oil is not limited to such viscosities. Indeed, it will be appreciated that different viscosities could be used and / or preferable for a particular application.

[0047] In some embodiments, epoxidized oil is epoxidized soy oil (ESO). The ESO can have the following chemical structure:epoxidized soy oil

[0048] The ESO can be made from soy oil (e.g., soybean oil). Soybean oils, as is known in the art, are common vegetable oils and typically include unsaturated fatty acid chains such as linolenic acid chains, linoleic acid chains, and oleic acid chains, and saturated fatty acid chains such as stearic acid chains and palmitic acid chains.

[0049] The epoxidized oil can be combined, in certain embodiments, with a non-expoidized oil including, without limitation, non-epoxidized versions of any of the oils listed herein. For example, if the epoxidized oil is combined with a non-epoxidized oil, the combination can include about 50%-95% EO by weight, about 55% EO by weight, about 55%-90% EO by weight, about 60% EO by weight, about 60%-85% EO by weight, about 65% EO by weight, about 65%-80% EO by weight, about 70% EO by weight, at least about 70%-75% EO by weight, about 75% EO by weight, about 80% EO by weight, about 85% EO by weight, about 90% EO by weight, or about 95% EO by weight. The percent ranges specified herein are inclusive of the stated end points.

[0050] In certain embodiments, soy oil can be obtained from soybean plants, whereas nucleophiles and phenolic compounds can be obtained from other sustainable natural sources. Thus, the adhesive can be non-toxic and debondable. In certain embodiments, one or more of the components of the adhesive composition can be synthetic.

[0051] The nucleophile is any suitable nucleophile that is sufficiently nucleophilic to open an epoxy ring on the epoxidized oil when mixed therewith. In certain embodiments, the nucleophile is bio-based. In certain embodiments, the nucleophile is a multifunctional nucleophile. In certainembodiments, the nucleophile comprises at least two functional groups to facilitate crosslinking reactions with the epoxidized oil.

[0052] In certain embodiments, the nucleophile comprises water, a urea, a hydroxyl-containing compound, an amine-containing compound, an amide-containing compound, a sulfhydryl- containing compound, or a mixture thereof. In certain embodiments, the nucleophile comprises glycerin. The nucleophile can be a polyamine. Certain examples of nucleophiles include, but are not limited to, compounds comprising a moiety selected from the group consisting of an acid, an alcohol, an amine, and a thiol. In some embodiments, the nucleophile is selected from fumaric acid, adipic acid, azelic acid, dodecanoic acid, itaconic acid, phthalic acid, oxalic acid, tartartic acid, sorbitol, sucrose, xylitol, glycerol, malic acid, maleic acid, succinic acid, or a combination thereof. In exemplary embodiments, the nucleophile is malic acid or an analog thereof. As used herein, “analog” means a compound that has a similar chemical structure to another compound, but differs from it by one or more particular components e.g., as in substitution of one atom by an atom of a different element, or a substitution of one or more functional groups by another functional group). Malic acid can comprise the following chemical structure:malic acid

[0053] In certain embodiments, the nucleophile comprises glycerol comprising the following chemical structure or an analog thereof:

[0054] The adhesive composition can comprise one or more different nucleophiles.

[0055] As noted above, the adhesive composition further comprises a phenolic compound. In certain embodiments, the adhesive composition can comprise one or more different phenolic compounds.

[0056] The term "phenolic compound" means a compound having a chemical structure that comprises a hydroxyl-substituted aromatic ring. The aromatic ring can be substituted with one or more hydroxyl groups. In certain embodiments, a phenolic compound comprises a hydroxylsubstituted aiyl group. In certain embodiments, the aryl group is a mono- or bicyclic aryl. A "phenolic compound" can also include polyphenol, which can have more than one hydroxyl-substituted aromatic rings (e.g., with one or more hydroxyl groups attached to the more than one aromatic rings). In certain embodiments, the phenolic compound comprises at least two hydroxyl groups. In certain embodiments, the phenolic compound comprises at least three hydroxyl groups. In certain embodiments, the phenolic compound comprises 2 or 3 hydroxyl groups.

[0057] The phenolic compound can be selected from catechol, gallic acid, galloL lignin, tannic acid, caffeic acid, 3,4-dihydroxybenzadehyde, 3,4-dihydroxybenzoic acid, juglone, quercitin, vanillin, (+) catechin hydrate, or comprise any combination of two or more of the foregoing. In certain embodiments, the phenolic compound comprises at least one catechol group comprising the following chemical structure or an analog thereof:

[0058] In certain embodiments, the phenolic compound comprises a gallic acid comprising the following chemical structure or an analog thereof:

[0059] In certain embodiments, the phenolic compound is obtained from a suistainable natural source and comprises a flavonoid such as a flavonol, a flavone, flavan-3ol (catechin), anthocyanidin, and / or an isoflavonoid. In certain embodiments, a naturally occurring phenolic compound comprises cannabinoids, capsaicin, carvacrol, cresol, estradiol, eugenol, gallic acid, guaiacol, methyl salicylate, raspberry ketone, salicylic acid, serotonin, thymol, tyrosine, sesamol, or a combination of any of the foregoing. In certain embodiments, the phenolic compound comprises a phenol, a bisphenol A, butylated hydroxytoluene, 4-nonylphenol, orthophenyl phenol, picric acid, phenolphthalein, xylenol, or a combination of two or more of the foregoing.

[0060] An example of a suitable phenolic compound for use herein is tannic acid or an anlog thereof. Tannic acid comprises reactive terminal phenolic hydroxyl groups with a hyperbranched aromatic / alicyclic polyester core, which can form highly cross-linked networks with one or more active epoxy groups of the EO (e.g., ESO, which has at least one highly active epoxy group). Tannic acid can comprise the following chemical structure:tannic acid

[0061] In some embodiments, the EO, nucleophile, and phenolic compound can be present in a mass ratio of about (0.1-10):(0.1-10):(0.1-10). In certain embodiments, the EO:nucleophile:phenolic compound mass ratio of the adhesive composition is about 1:10:10. In certain embodiments, the EO:nucleophile:phenolic compound mass ratio of the adhesive composition is about 0.1:10:10, about 0.2:10:10, about 0.3:10:10, about 0.4:10:10, about 0.5:10:10, about 0.6:10:10, about 0.7:10:10, about 0.8:10:10, about 0.9:10:10, about 1.1:10:10, about 1.2:10:10, about 1.3:10:10, about 1.4:10:10, about 1.5:10:10, about 1.6:10:10, about 1.7:10:10, about 1.8:10:10, about 1.9:10:10, about 2:10:10, about 2.1:10:10, about 2.2:10:10, about 2.3:10:10, about 2.4:10:10, about 2.5:10:10, about 2.6:10:10, about 2.7:10:10, about 2.8:10:10, about 2.9:10:10, about 3:10:10, about 3.1:10:10, about 3.2:10:10, about 3.3:10:10, about 3.4:10:10, about 3.5:10:10, about 3.6:10:10, about 3.7:10:10, about 3.8:10:10, about 3.9:10:10, about 4:10:10, about 4.1:10:10, about 4.2:10:10, about 4.3:10:10, about 4.4:10:10, about 4.5:10:10. about 4.6:10:10, about 4.7:10:10, about 4.8:10:10, about 4.9:10:10, about 5:10:10, about 5.1:10:10, about 5.2:10:10, about 5.3:10:10, about 5.4:10:10, about 5.5:10:10, about 5.6:10:10, about 5.7:10:10, about 5.8:10:10, about 5.9:10:10, about 6:10:10, about6.1:10:10, about 6.2:10:10, about 6.3:10:10, about 6.4:10:10, about 6.5:10:10, about 6.6:10:10, about 6.7:10:10, about 6.8:10:10, about 6.9:10:10, about 7:10:10, about 8.1:10:10, about 8.2:10:10, about 8.3:10:10, about 8.4:10:10, about 8.5:10:10, about 8.6:10:10, about 8.7:10:10, about 8.8:10:10. about 8.9:10:10, about 9:10:10, about 9.1:10:10. about 9.2:10:10, about 9.3:10:10, about 9.4:10:10, about 9.5:10:10, about 9.6:10:10, about 9.7:10:10, about 9.8:10:10, about 9.9:10:10, or about 10:10:10. In certain embodiments, the EO: nucleophile: phenolic compound mass ratio of the adhesive composition is about 10:0.1:10, about 10:0.2:10, about 10:0.3:10, about 10:0.4:10, about 10:0.5:10, about 10:0.6:10, about 10:0.7:10, about 10:0.8:10, about 10:0.9:10, 10:1.1:10, about 10:1.2:10, about 10:1.3:10, about 10:1.4:10, about 10:1.5:10, about 10:1.6:10, about 10:1.7:10, about 10:1.8:10, about 10:1.9:10, about 10:2:10, about 10:2.1:10, about 10:2.2:10, about 10:2.3:10, about 10:2.4:10, about 10:2.5:10, about 10:2.6:10, about 10:2.7:10, about 10:2.8:10, about 10:2.9:10, about 10:3:10, about 10:3.1:10, about 10:3.2:10, about 10:3.3:10, about 10:3.4:10, about 10:3.5:10, about 10:3.6:10, about 10:3.7:10, about 10:3.8:10. about 10:3.9:10, about 10:4:10, about 10:4.1:10, about 10:4.2:10, about 10:4.3:10, about 10:4.4:10, about 10:4.5:10, about 10:4.6:10, about 10:4.7:10, about 10:4.8:10, about 10:4.9:10, about 10:5:10, about 10:5.1:10, about 10:5.2:10, about 10:5.3:10, about 10:5.4:10, about 10:5.5:10, about 10:5.6:10, about 10:5.7:10, about 10:5.8:10, about 10:5.9:10, about 10:6:10, about 10:6.1:10, about 10:6.2:10, about 10:6.3:10. about 10:6.4:10, about 10:6.5:10, about 10:6.6:10, about 10:6.7:10, about 10:6.8:10, about 10:6.9:10, about 10:7:10, about 10:8.1:10, about 10:8.2:10, about 10:8.3:10, about 10:8.4:10, about 10:8.5:10, about 10:8.6:10, about 10:8.7:10, about 10:8.8:10, about 10:8.9:10, about 10:9:10, about 10:9.1:10, about 10:9.2:10. about 10:9.3:10, about 10:9.4:10, about 10:9.5:10, about 10:9.6:10, about 10:9.7:10, about 10:9.8:10, or about 10:9.9:10. In certain embodiments, the EO:nucleophile:phenolic compound mass ratio of the adhesive composition is about 10:10:0.1, about 10:10:0.2, about 10:10:0.3, about 10:10:0.4, about 10:10:0.5, about 10:10:0.6, about 10:10:0.7, about 10:10:0.8, about 10:10:0.9, 10:10:1.1, about 10:10:1.2, about 10:10:1.3, about 10:10:1.4, about 10:10:1.5, about 10:10:1.6, about 10:10:1.7, about 10:10:1.8, about 10:10:1.9, about 10:10:2, about 10:10:2.1, about 10:10:2.2, about 10:10:2.3, about 10:10:2.4, about 10:10:2.5, about 10:10:2.6, about 10:10:2.7, about 10:10:2.8, about 10:10:2.9, about 10:10:3, about 10:10:3.1, about 10:10:3.2, about 10:10:3.3, about 10:10:3.4:10, about 10:10:3.5, about 10:10:3.6, about 10:10:3.7, about 10:10:3.8, about 10:10:3.9. about 10:10:4, about 10:10:4.1, about 10:10:4.2, about 10:10:4.3, about 10:10:4.4, about 10:10:4.5, about 10:10:4.6, about 10:10:4.7, about 10:10:4.8, about 10:10:4.9, about 10:10:5, about 10:10:5.1, about 10:10:5.2, about 10:10:5.3, about 10:10:5.4, about 10:10:5.5, about 10:10:5.6, about 10:10:5.7, about 10:10:5.8, about 10:10:5.9, about 10:10:6, about 10:10:6.1, about 10:10:6.2, about 10:10:6.3,about 10:10:6.4, about 10:10:6.5, about 10:10:6.6, about 10:10:6.7, about 10:10:6.8, about 10:10:6.9, about 10:10:7, about 10:10:8.1, about 10:10:8.2, about 10:10:8.3, about 10:10:8.4, about 10:10:8.5, about 10:10:8.6, about 10:10:8.7, about 10:10:8.8, about 10:10:8.9, about 10:10:9, about 10:10:9.1, about 10:10:9.2, about 10:10:9.3, about 10:10:9.4, about 10:10:9.5, about 10:10:9.6, about 10:10:9.7, about 10:10:9.8, or about 10:10:9.9. In certain embodiments, the EO: nucleophile: phenolic compound mass ratio of the adhesive composition is about 1- 10:10:0.1, about 1-10:10:0.2, about 1-10:10:0.3, about 1-10:10:0.4, about 1-10:10:0.5, about 1- 10:10:0.6, about 1-10:10:0.7, about 1-10:10:0.8, about 1-10:10:0.9, 1-10:10:1.1, about 1- 10:10:1.2, about 1-10:10:1.3, about 1-10:10:1.4, about 1-10:10:1.5, about 1-10:10:1.6, about 1-10:10:1.7, about 1-10:10:1.8, about 1-10:10:1.9, about 1-10:10:2, about 1-10:10:2.1, about 1-10:10:2.2, about 1-10:10:2.3, about 1-10:10:2.4, about 10:10:2.5, about 1-10:10:2.6, about 1-10:10:2.7, about 1-10:10:2.8, about 1-10:10:2.9, about 1-10:10:3, about 1-10:10:3.1, about 1-10:10:3.2, about 1-10:10:3.3, about 1-10:10:3.4:10. about 1-10:10:3.5, about 1-10:10:3.6, about 1-10:10:3.7, about 1-10:10:3.8, about 1-10:10:3.9, about 1-10:10:4, about 1-10:10:4.1, about 1-10:10:4.2, about 1-10:10:4.3, about 1-10:10:4.4, about 1-10:10:4.5, about 1-10:10:4.6, about 1- 10:10:4.7, about 1-10:10:4.8, about 1-10:10:4.9, about 10:10:5, about 1-10:10:5.1, about 1- 10:10:5.2, about 1-10:10:5.3, about 1-10:10:5.4, about 1-10:10:5.5, about 1-10:10:5.6, about 10:10:5.7, about 10:10:5.8, about 10:10:5.9, about 10:10:6, about 10:10:6.1, about 1-10:10:6.2, about 1-10:10:6.3, about 1-10:10:6.4, about 1-10:10:6.5, about 1-10:10:6.6, about 1-10:10:6.7, about 1-10:10:6.8, about 1-10:10:6.9, about 1-10:10:7, about 1-10:10:8.1, about 1-10:10:8.2, about 10:10:8.3, about 1-10:10:8.4, about 1-10:10:8.5, about 1-10:10:8.6, about 1-10:10:8.7, about 1-10:10:8.8, about 1-10:10:8.9, about 1-10:10:9, about 1-10:10:9.1, about 1-10:10:9.2, about 1-10:10:9.3, about 1-10:10:9.4, about 1-10:10:9.5. about 1-10:10:9.6, about 1-10:10:9.7, about 1-10:10:9.8, or about 1-10: 10:9.9. In certain embodiments, the EO:nucleophile:phenolic compound mass ratio of the adhesive composition is about 0.1 :(l-10): 10, about 0.2:(l-10):10, about 0.3:(l-10): 10, about 0.4:(l-10): 10, about 0.5:(l-10): 10, about 0.6:(l-10):10. about 0.7:(l- 10): 10. about 0.8:(l-10): 10, about 0.9:(l-10): 10, about 1.1 :(l-10): 10, about 1.2:(l-10): 10. about 1.3:(l-10):10, about 1.4:(l-10): 10, about 15:(l-10): 10, about 1.6:(l-10): 10, about 17:(l-10): 10, about 1.8:(l-10): 10, about 19:(l-10): 10, about 2:(l-10):10, about 2.1 :(l-10): 10, about 2.2:(1- 10):10, about 2.3:(l-10):10, about 2.4:(l-10): 10, about 2.5:(l-10): 10, about 2.6:(l-10): 10, about 2.7:(l-10): 10, about 2.8:(l-10): 10, about 2.9:(l-10): 10, about 3:(l-10): 10, about 3.1:(l-10): 10, about 3.2:10:10, about 3.3:(l-10): 10, about 3.4:(l-10): 10, about 3.5 :( 1- 10): 10, about 3.6:(1- 10):10, about 3.7:(1-10): 10, about 3.8:(1-10): 10, about 3.9:(l-10): 10, about 4:(l-10):10, about 4.1:(l-10):10, about 4.2:(l-10): 10, about 4.3:(l-10): 10, about 4.4:(l-10): 10, about 4.5:(l-10): 10, about 4.6:(l-10):10, about 4.7:(l-10):10, about 4.8:(l-10):10, about 4.9:(l-10):10, about 5:(1-10): 10, about 5. 1 :(l-10): 10, about 5.2:(l-10): 10, about 5.3:(l-10): 10, about 5.4:(l-10): 10, about 5.5:(l-10):10, about 5.6: 10:10, about 5.7:(l-10): 10, about 5.8:(l-10): 10, about 5.9:(l-10): 10, about 6:(l-10):10, about 6. 1 :(l-10): 10, about 6.2:(l-10): 10, about 6.3:(l-10): 10, about 6.4:(1- 10): 10, about 6.5:(l-10): 10, about 6.6:(l-10): 10, about 6.7:(l-10): 10, about 6.8:(l-10): 10, about 6.9:(l-10): 10, about 7:(l-10): 10, about 8.1 :(l-10): 10, about 8.2:(l-10): 10, about 8.3:(l-10): 10, about 8.4:(l-10): 10, about 8.5:(l-10): 10, about 8.6:(l-10): 10, about 8.7:(l-10): 10, about 8.8:(1- 10): 10, about 8.9:(l-10): 10, about 9:(l-10): 10, about 9. 1 :(l-10): 10, about 9.2:(l-10): 10, about 9.3:(l-10): 10, about 9.4:(l-10): 10, about 9.5:(l-10): 10, about 9.6:(l-10): 10, about 9.7:(l-10): 10, about 9.8: (1-10): 10, or about 9.9: (1 -10): 10. In certain embodiments, the EO:nucleophile:phenolic compound mass ratio of the adhesive composition is about 10:0.1 :(1 -10), about I0:0.2:(l-l 0), about 10:0.3 :(1-10), about 10:0.4:(l-10), about 10:0.5:(l-10), about 10:0.6:(l-10), about 10:0.7:(l-10), about 10:0.8:(l-10), about 10:0.9:(l -10), 10: 1.1 :(l-10), about 10: 1 ,2:(l-10), about 10: 1 ,3:(l-10), about 10: 1 ,4:(l-10), about 10: 1.5:(1 -10), about 10: 1 6:(l-10), about 10: 1 ,7:(l-10), about 10: 1.8:(l-10), about 10: 1 ,9:(l-10), about 10:2:(l-10), about 10:2. 1 :(l-10), about 10:2.2:(l- 10), about 10:2.3:(l-10), about 10:2.4:(l-10), about 10:2.5:(l-10), about 10:2.6:(l-10), about 10:2.7:(l-10), about 10:2.8:(l-10), about 10:2.9:(l-10), about 10:3:(l-10), about 10:3. l:(l-10), about 10:3.2:(l-10), about 10:3.3: (1 -10), about 10:3.4:(l-10), about 10:3.5:(l-10), about10:3.6:(l-10), about 10:3.7:(l-10), about 10:3.8:(l-10), about 10:3.9:(l-10), about 10:4:(l-10), about 10:4.1 :( 1- 10), about 10:4.2:(l-10), about 10:4.3:(l-10), about 10:4.4:(l-10), about10:4.5:(l-10), about 10:4.6:(l-10), about 10:4.7:(l -10), about 10:4.8:(l-10), about 10:4.9:(l-10), about 10:5:(l-10), about 10:5. 1 :(l-10), about 10:5.2:(l-10), about 10:5.3:(l-10), about 10:5.4:(l- 10), about 10:5.5:(l-10), about 10:5.6:(l-10), about 10:5.7:(l-10), about 10:5.8:(l-10), about 10:5.9:(l-10), about 10:6:(l-10), about 10:6.1 :(l-10), about 10:6.2:(l-10), about 10:6.3:(l-10), about 10:6.4:(l-10), about 10:6.5:(l-10), about 10:6.6:(l-10), about 10:6.7:(l-10), about 10:6.8:(l-10), about 10:6.9:(l-10), about 10:7:(l-10), about 10:8. l:(l-10), about 10:8.2:(l-10), about 10:8.3:(l-10), about 10:8.4:(l-10), about 10:8.5:(l-10), about 10:8.6:(l-10), about10:8.7:(l-10), about 10:8.8:(l-10), about 10:8.9:(l-10), about 10:9:(l-10), about 10:9. 1 :(l-10), about 10:9.2:( 1-10), about 10:9.3:(l-10), about 10:9.4:(l-10), about 10:9.5:(l-10), about10:9.6:(l-10), about 10:9.7, about 10:9.8:(l-10), or about 10:9.9:(l-10). The ranges specified herein are inclusive of the stated end points and specifically include all 0.1 increments within the specified ranges.

[0062] In certain embodiments, the adhesive composition mass ratios listed herein can be convertred to grams of components. In certain embodiments, the adhesive composition comprises at or about 1 gram of epoxidized oil: 0.4 grams of nucleophile: 0.5 grams phenolic compound. In certain embodiments, the phenolic compound can comprise 0.5 grams / ml of phenolic compoundin solvent. In certain embodiments, the adhesive composition comprises at or about 1 gram of epoxidized oil: (0.3-0.6 grams of nucleophile): (0.3-0.6 grams phenolic compound). These amounts and / or ranges can be scaled, for example, by at least a magnitude of 10-100. In certain embodiments, the adhesive composition comprises at or about 100 grams of epoxidized oil: 30- 60 grams of nucleophile: 30-60 grams of phenolic compound. In certain embodiments, the adhesive composition comprises at or about (0.1-10 grams of epoxidized oil):(0. 1-10 grams of nuclophile): (0.1-10 grams of phenolic compound). In certain embodiments, 50-100 grams of epoxidized oil: 15-60 grams of nuclophile: 15-60 grams of phenolic compound. In certain embodiments, the adhesive composition comprises at or about 100 grams of epoxidized oil: 30- 60 grams of nucleophile: 30-60 grams of phenolic compound. In certain embodiments, 9-10 grams of epoxidized oil: 4-5 grams of nuclophile: 3-6 grams of phenolic compound. The ranges specified herein are inclusive of the stated end points and specifically include all 0.1 increments within the specified ranges.

[0063] In some embodiments, the epoxidized oil, nucleophile, and phenolic compound are present in the mass ratio of about l:(0.3-0.6):(0.3-0.6), respectively. The ranges specified in the immediately preceding sentence are inclusive of the stated end points and specifically include all 0.1 increments within the specified ranges. In certain embodiments, the EO. nucleophile, and phenolic compound are present in the mass ratio of about 1:0.4:0.5 (such as 1:0.4:0.5), respectively. In certain embodiments, the EO, nucleophile, and phenolic compound are present in the mass ratio of about l :0.4:0.5 (such as 1 :0.4:0.5), respectively, wherein the adhesive composition further comprises about 0.4 grams (e.g., 0.4 grams) of solvent for use in solubilizing the phenolic compound.

[0064] In some embodiments, provided is an adhesive composition comprising (i) an ESO (ii) a malic acid, and (iii) a tannic acid ('‘soy-mal-tan”). It is understood that each of the foregoing recitations of ratios and concentrations is applicable to this exemplary emobidment. For sake of illustration, the ESO, malic acid, and tannic acid can be present in a mass ratio of about 1:0.1 :0.1 to about 1 : 10: 10 (such as about EO. EO. l to 1: 10: 10, EO. EO. l to about 1 : 10: 10 or EO. EO. l to 1 : 10: 10). In some embodiments, ESO, malic acid, and tannic acid can be present in a mass ratio of about l:(0.3-0.6):(0.3-0.6) (such as l:(0.3-0.6):(0.3-0.6)), wherein the ranges specified are inclusive of the stated end points and specifically include all 0.1 increments within the specified ranges. In certain embodiments, the EO comprises ESO, the nucleophile comprises glycol (gly), and the phenolic compound comprises tannic acid (tan), which are present in a soy-mal-tan mass ratio of about l :0.4:0.6 (such as l :0.4:0.6). In certain embodiments, the EO comprises ESO (soy), the nucleophile comprises glycol (gly), and the phenolic compound comprises tannic acid (tan), which are present in a soy-gly-tan mass ratio of about 1 :0.6:0.4 (such as l:0.6:0.4). In certainembodiments, the EO comprises ESO (soy), the nucleophile comprises malic acid (mal), and the phenolic compound comprises tannic acid (tan), which are present in a soy-mal-tan mass ratio of about 1:0.4:0.5 (such as l:0.4:0.5). In certain embodiments, the EO comprises ESO (soy), the nucleophile comprises malic acid (mal), and the phenolic compound comprises tannic acid (tan), which are present in a soy-mal-tan mass ratio of about 1 :0.4:0.3 (such as l :0.4:0.3).

[0065] Combining the epoxidized oil, the nucleophile, and the phenolic compound of the adhesive composition can form covalent bonds and highly cross-linked matrices, which contribute to high- strength adhesion.

[0066] The adhesive composition can further comprise a solvent. The use of the solvent in the adhesive composition can be optional. In certain embodiments thereof, the adhesive composition consists essentially of an epoxidized oil (EO), at least one nucleophile, at least one phenolic compound, and a solvent.

[0067] The solvent can be an aqueous and / or organic solvent. The solvent can comprise any solvent suitable to solubilize at least the phenolic compound of the adhesive composition when added thereto. The solvent can comprise water. The solvent can comprise an alcohol. The solvent can comprise an alcohol and water. Examples of suitable solvents include, but are not limited to, alcohols such as ethanol or methanol, acetone, ammonia, ethyl acetate, hexane, heptane, tetrahydrofuran, acetonitrile, toluene, glycol ethers, chloroform, dichloromethane, dimethyl sulfoxide, dimethyl formamide, and the like. In some embodiments, the solvent is ethanol.

[0068] In some embodiments, the adhesive composition can include the solvent when the phenolic compound is not readily soluble in a mixture of the phenolic compound, nucleophile, and epoxidized oil. A solvent can increase the reactivity of the the epoxidized oil, the nucleophile, and the phenolic compound within the mixture, thereby facilitating, in certain instances, the formation of covalent bonds and highly cross-linked matrices and, thus, stronger bonds therebetween. In certain embodiments, for example, it can be beneficial for the adhesive composition to comprise a solvent where the phenolic compound comprises tannic acid. In certain embodiments, any suitable solvent that solubilizes tannic acid can be used (e.g, when the phenolic compound of the adhesive composition comprises tannic acid).

[0069] In some embodiments, the alcohol is ethanol or methanol. The amount of organic solvent, such as ethanol, present in an amount sufficient to solubilize tannic acid or another phenolic compound in the adhesive composition.

[0070] In certain embodiments, the amount of solvent present in the adhesive composition is at or between about 0.2 grams - 1.2 gram for each gram of combined epoxidized oil, nucleophile, and phenolic compound (such range inclusive of the stated end points and specifically including all 0. 1 gram increments within the specified range). In certain embodiments, each 1 gram of adhesivecomposition comprises about 0.7 grams of combined epoxidized oil, nucleophile, and phenolic compound and about 0.3 grams of solvent. In certain embodiments, each 1 gram of adhesive composition comprises about 0.5-0.9 grams of combined epoxidized oil, nucleophile, and phenolic compound (such as 0.5-0.9 grams of combined epoxidized oil, nucleophile, and phenolic compound) and about 0.5-0. 1 grams of solvent (such as 0.5-0. 1 grams of solvent).

[0071] In certain embodiments, the amount of solvent present in the adhesive composition is about 0.2 grams (such as 0.2 grams), about 0.3 grams (such as 0.3 grams), about 0.4 grams (such as 0.4 grams), about 0.5 grams (such as 0.5 grams), about 0.6 grams (such as 0.6 grams), about 0.7 grams (such as 0.7 grams), about 0.8 grams (such as 0.8 grams), about 0.9 grams (such as 0.9 grams), about 1.0 gram (such as 1.0 gram), about 1.1 grams (such as 1.1 grams), or about 1.2 grams (such as 1.2 grams) for each 1.0 gram of combined epoxidized oil, nucleophile, and phenolic compound (e.g., soy-mal-tan). In embodiments thereof, the adhesive composition consists essentially of, or consists of. soy-mal-tan and ethanol.

[0072] The amount of solvent (or lack thereof) in the adhesive composition can be modified to achieve a desired viscosity of the adhesive solution. In certain embodiments, the adhesive composition (i.e., uncured) has a viscosity of from about 1,200 to about 7,000 cps at 25 °C (such as 1,200 to about 7,000, about 1,200 to 7,000, or 1,200 to 7,000 cps at 25 °C). In certain embodiments, the adhesive composition (i.e., uncured) has a viscosity of from about 1,200 to about 3,000 cps at 25 °C (such as 1,200 to about 3,000, about 1,200 to 3,000, or 1,200 to 3,000 cps at 25 °C). In certain embodiments, the adhesive composition (i.e., uncured) has a viscosity of from about 3,000 to about 5,000 cps at 25 °C (such as 3,000 to about 5,000, about 3,000 to 5,000, or 3,000 to 5,000 cps at 25 °C). In certain embodiments, the adhesive composition (i.e., uncured) has a viscosity of from about 4,000 to about 7,000 cps at 25 °C (such as 4,000 to about 7,000, about 4,000 to 7,000, or 4,000 to 7,000 cps at 25 °C). In certain embodiments, the adhesive composition has a viscosity7of at or about 150-400 cps at 25 °C. In certain embodiments, the adhesive has a viscosity of at or about 200-1.200 cps at 25 °C. In certain embodiments, the adhesive composition has a viscosity as low as 100 cps at 75 °C. In certain embodiments, the adhesive composition has a viscosity as high as 150 cps at 75 °C. In certain embodiments, the adhesive composition has a viscosity7as high as 500,000 cps at 25 °C. In certain embodiments, the adhesive composition has a viscosity as high as 1,000,000 cps at 25 °C. In certain embodiments, the adhesive composition has a viscosity as high as 1.500,000 cps at 25 °C. The ranges specified in this paragraph are inclusive of the stated end points and specifically include all 1 cps increments within the specified range.

[0073] The adhesive composition can be manufactured by reacting the EO, nucleophile, and phenolic compound. The EO, nucleophile (e.g., malic acid) and phenolic compound (e.g., tannicacid) of the adhesive composition can be reacted together to obtain an adhesive (e.g., soy-mal- tan). In some embodiments, the reaction of the three components together can yield a high-strength and sustainably sourced adhesive.

[0074] In certain embodiments, the adhesive (z.e., the adhesive composition when cured) has an adhesive strength / value of about 1.5-2.0 MPa, about 2.0-3.0 MPa, 3.0-4.0 MPa. about 4.0-5.0 MPa, about 5.0-6.0 MPa, about 6.0-7.0 MPa, about 6.5-7.0 MPa, about 7.0-7.5 MPa, about 7.5- 8.0 MPa, about 8.0-8. MPa, about 8.5-9.0 MPa, about 9.0-9.5 MPa, about 9.5-10.0 MPa, about 10-15 MPa, or about 15-20 MPa (wherein the ranges specified herein are inclusive of the stated end points and specifically include all 0. 1 increments within the specified ranges). As used herein, “adhesive strength refers to the force that maintains different materials (i.e., substrates) together at their interfaces. The adhesive strength can vary depending on multiple factors including, for example, the substrate(s) to which the adhesive is applied and / or the conditions under which the adhesive is cured (as described in additional detail below).

[0075] In certain embodiments, the adhesive has a tensile strength of about 10 MPa (such as 10 MPa). In certain embodiments, the adhesive has a tensile strength of about 13 MPa (such as 13MPa). In certain embodiments, the adhesive has a tensile strength of about 14 MPa (such as 14MPa). In certain embodiments, the adhesive has a tensile strength of about 15 MPa (such as 15MPa). In certain embodiments, the adhesive has a tensile strength of about 16 MPa (such as 16MPa). In certain embodiments, the adhesive has a tensile strength of about 18 MPa (such as 18MPa). In certain embodiments, the adhesive has an adhesion value of about 1.5 MPa (such as 1.5 MPa). In certain embodiments, the adhesive has an adhesion value of about 4. 1 MPa (such as 4. 1 MPa).

[0076] Also provided is a method of formulating the adhesive composition hereof. The adhesive composition can be any of the adhesive compositions described herein. In certain embodiments, the adhesive composition comprises an epoxidized oil, one or more nucleophiles, and one or more phenolilc compounds. Optionally, the adhesive composition can further comprise a solvent.

[0077] To form the adhesive composition via a precursor reaction, the method can comprise: i) heating an epoxidized oil (EO); ii) mixing a phenolic compound with the epoxidized oil of step (i) to obtain an EO solution or mixture, wherein the phenolic compound is optionally in the form of a solution in a solvent (if present); iii) adding a nucleophile to the EO solution or mixture of step (ii) and heating said resulting reaction mixture; and iv) cooling the reaction mixture (or allowing the reaction mixture to cool) to at or about room temperature (e.g., at or about 18 °C to about 25 °C (such asabout 18 °C to 25 °C, about 18 °C to 25 °C, or 18 °C to 25 °C, inslucisve of the stated end points and all 0.1 °C increments within the specified ranges)), whereupon the adhesive composition (e.g. , a shelf-stable adhesive composition) is obtained.

[0078] The heating step(s) can be performed using standard heating methodologies, such as in a reaction flask heated by a heat source or using microwave frequency or ultrasound. The heat source can be a flame, a cartridge heater, an oven, a heat gun, a heatlamp (e.g., an infrared heatlamp), a laser beam, or any other heat source suitable to apply heat to the epoxidized oil and / or mixture comprising the same. In certain embodiments, the heat source is an electric heat source. In certain embodiments, the heat source is a hair dryer or other external heat source.

[0079] In certain embodiments, one or both of the heating steps (z.e., (i) and (iii)) can be performed under nitrogen atmosphere. In certain embodiments, the EO is not heated at step (i), but instead the phenolic compound is added to ambient or room temperature EO at step (ii).

[0080] The epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of up to about 90 °C, such as from about room temperature (z.e., about 20-22 °C) to 90 °C or to about 90 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 25 °C to about 90 °C, such as about 25 °C to 90 °C, 25 °C to about 90 °C, or 25 °C to 90 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 30 °C to about 90 °C, such as about 30 °C to 90 °C, 30 °C to about 90 °C, or 30 °C to 90 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 35 °C to about 90 °C, such as about 35 °C to 90 °C, 35 °C to about 90 °C, or 35 °C to 90 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 40 °C to about 85 °C, such as about 40 °C to 85 °C, 40 °C to about 85 °C, or 40 °C to 85 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 45 °C to about 75 °C, such as about 45 °C to 75 °C, 45 °C to about 75 °C, or 45 °C to 75 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the sameor different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 50 °C to about 70 °C, such as about 50 °C to 70 °C, 50 °C to about 70 °C, or 50 °C to 70 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of up to about 70 °C, such as from about room temperature (i.e., about 20-22 °C) to 70 °C or to about 70 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 55 °C to about 65 °C, such as about 55 °C to 65 °C, 55 °C to about 65 °C, or 55 °C to 65 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. In certain embodiments, the epoxidized oil and / or the reaction mixture of epoxidized oil, nucleophile(s), and phenolic compound(s) can be heated to a temperature of about 40 °C to about 65 °C, such as about 40 °C to 65 °C, 40 °C to about 65 °C, or 40 °C to 65 °C at steps (i) and / or (iii), wherein the temperature at (i) and (iii) can be the same or different. The ranges specified herein are inclusive of the stated end points and specifically include all 1 °C increments within the specified ranges.

[0081] The temperature of the heated epoxidized oil at step (i) can be, in certain embodiments, held at or about a set temperature while the desired amounts of the phenolic compound and nucleophile are added to the mixture at steps (ii) and (iii). The reaction mixture comprising epoxidized oil, nucleophile, and phenolic compound (and optionally solvent) can then be thoroughly mixed and heated to and / or maintained at approximately a set temperature of up to about 90 °C, such as from about room temperature (i.e., about 20-22 °C) to about 90 °C (such as 90 °C) at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 25 °C to about 90 °C, such as about 25 °C to 90 °C, 25 °C to about 90 °C, or 25 °C to 90 °C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 30 °C to about 90 °C, such as about 30 °C to 90 °C, 30 °C to about 90 °C, or 30 °C to 90 °C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 35 °C to about 90 °C, such as about 35 °C to 90 °C, 35 °C to about 90 °C, or 35 °C to 90 °C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 40 °C to about 85 °C, such as about 40 °C to 85 °C, 40 °C to about 85 °C, or 40 °C to 85 °C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 45 °C to about 75 °C, such as about 45 °C to 75 °C, 45 °C to about 75 °C, or 45 °C to 75 °C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 50 °C to about 70 °C, such as about 50 °C to 70 °C, 50 °C to about 70 °C, or 50 °C to 70°C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of up to about 70 °C, such as from about room temperature (i.e., about 20-22 °C) to 70 °C or to about 70 °C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 55 °C to about 65 °C, such as about 55 °C to 65 °C, 55 °C to about 65 °C, or 55 °C to 65 °C at step (iii). In certain embodiments, the reaction mixture can be heated to a temperature of about 40 °C to about 65 °C, such as about 40 °C to 65 °C, 40 °C to about 65 °C, or 40 °C to 65 °C at step (iii). The ranges set forth in this paragraph are inclusive of the stated end points and all 0. 1 °C increments within the specified ranges. In certain embodiments, the mixture is heated to and held at a set temperature of about 70 °C, such as about 70 °C.

[0082] The reaction mixture can be held at the set temperature for about 6 hours to about 24 hours, such as about 6 hours to 24 hours, 6 hours to about 24 hours, or 6 hours to 24 hours (specified ranges inclusive of the stated end points and all 15 minute increments within the specified ranges). The reaction mixture can be held at the set temperature for about 8 hours to about 22 hours, such as about 8 hours to 22 hours, 8 hours to about 22 hours, or 8 hours to 22 hours. The reaction mixture can be held at the set temperature for about 10 hours to about 20 hours, such as about 10 hours to 20 hours, 10 hours to about 20 hours, or 10 hours to 20 hours. The reaction mixture can be held at the set temperature for about 12 hours to about 18 hours, such as about 12 hours to 18 hours, 12 hours to about 18 hours, or 12 hours to 18 hours. The reaction mixture can be held at the set temperature for about 14 hours to about 16 hours, such as about 14 hours to 16 hours, 14 hours to about 16 hours, or 14 hours to 16 hours. The reaction mixture can be held at the set temperature for at or about 24 hours. The ranges set forth in this paragraph are inclusive of the stated end points and all 30 minute increments within the specified ranges.

[0083] In each of steps (i)-(iv) of the method, the composition can bestatic, stirred or agitated. For example and without limitation, where step (iii) includes a period where the reaction mixture is heated to and / or held at a set temperature, the reaction mixture can be stirred or agitated for all or a portion thereof.

[0084] In certain embodiments, a vacuum can be applied to reduce any residual solvent that forms or is otherwise present. In certain embodiments, there need not be any additional workup of this initial precursor reaction. This precursor reaction is a simple mixing and heating process that can easily be performed on a large scale.

[0085] The phenolic compound(s) can be added to the epoxidized oil at step (ii). As noted above, this can be under heat or at ambient temperatures (e.g, at about 18 °C - 24 °C). The phenolic compound can be added dropwise, for example. The phenolic compound can be poured into epoxidized oil or otherwise added as is know n in the art.

[0086] In certain embodiments, a solvent can also be added at step (ii) either concurrently or sequentially with the phenolic compound(s). In certain embodiments, the solvent can be first mixed with the phenolic compound(s) to dissolve the same, and the solvent / phenolic compound solution is added to the epoxidized oil (e.g., heated epoxidized oil). Alternatively, the solvent and phenolic compound(s) can each be independently added to the epoxidized oil in which case, the entire mixture can be stirred to promote dissolution of the phenolic compound(s).

[0087] Notwithstanding the foregoing, the phenolic compound(s) need not necessarily be entirely soluble or dissolved within the epoxidized oil and / or solvent to achieve a successful adhesive composition. In certain embodiments, the phenolic compound(s) are not entirely soluble (or exhibit poor solubility ) in the epoxidized oil, however, are still available to react with the epoxidized oil and / or nucleophile(s).

[0088] The nucleophile(s) can be added to the epoxidized oil and phenolic compound mixture and / or solution at step (iii). As noted above, this can be under heat or at ambient temperatures (e.g., at about 18 °C-24 °C). The nuclephile can be added dropwise, for example.

[0089] In certain embodiments, two or more of steps (i), (ii), and (iii) are performed concurrently. In certain embodiments, steps (i), (ii), and (iii) are performed at substantially the same time; i.e., all components of the adhesive composition are simultaneously placed in a container and all three are heated and stirred together as described herein. Where the adhesive composition comprises a solvent, the solvent can similarly be added concurrently with the other components or, as described above, used first to dissolve the phenolic compound(s) prior to their addition to the epoxidized oil.

[0090] When all components of the adhesive composition are mixed and / or in solution, the mixture / solution is cooled at step (iv). In certain embodiments, the mixture / solution is actively cooled, for example, using a cooling device such as a refrigerator, a cooler, a fan, or the like. In certain embodiments, the mixture / solution is allowed to cool by being removed from the heat source. The solution / mixture is cooled to at or about room temperature (e.g. , at or about 18 °C to about 25 °C (such as about 18 °C to 25 °C, about 18 °C to 25 °C, or 18 °C to 25 °C, inslucisve of the stated end points and all 0.1 °C increments within the specified ranges), whereupon the adhesive composition (e.g., a shelf-stable adhesive composition) is obtained. While some bond formation may have begun between the components of the adhesive composition, it will be understood that the resulting adhesive composition remains viscous and not entirely cured such that it can easily be applied to one or more substrates.

[0091] The viscosity of the adhesive composition can be affected by several factors including, without limitation, the ratios and / or types of components used in the formulation thereof, the amount of time the precursor mixture is held at a set temperature, the temperature to which theprecursor reaction is heated, the number of times the precursor mixture / solution is heated, and / or the amount of time the precursor mixture / solution cools and / or otherwise is stored. Furthermore, the viscosity7of the adhesive composition (or components thereof) can change during performance of the method.

[0092] For example, adhesive compositions (or components thereof) that are slightly elevated in temperature can flow more readily than at room temperature. The viscosity of the adhesive composition generally can decrease at elevated temperatures until curing, at which point the visocity of the adhesive composition can increase.

[0093] Furthermore, in some embodiments, heating the EO to a temperature of about 70° C to about 90 °C can decrease the viscosity of the resultant adhesive composition (as compared to if the EO is not heated above ambient or room temperature at step (i)). The reaction at 70 °C for 24 hours can yield an amber-colored flowing gel adhesive composition for application between substrates or for use in other adhesive applications.

[0094] Desirability of a higher or lower viscosity can depend on the desired application. In certain embodiments, the viscosity of the adhesive composition can comprise a gel.

[0095] The heated material can be placed between substrates and cured to form the adhesive. In part, the components of the adhesive composition react with the expoxy groups of the epoxidized oil which can tend to cause a viscosity of the final cured adhesive to increase due to the formation of the dense cross-linked structure. The adhesive can be cured at about 20°C to about 180 °C such as about 20 °C to 180 °C, 20 °C to about 180 °C, or 20 °C to 180 °C for about 1 hour to about 24 hours, such as about 1 hour to 24 hours, 1 hour to about 24 hours, or 1 hour to 24 hours. In certain embodiments, a high bond strength can be achieved for the adhesive when cured at about 180 °C for about 24 hours. After curing (180 °C, 24 hours), the adhesive can become a hard, blackish solid. As used herein, ’‘bond strength” means the amount of adhesion between bonded surfaces. This is one measure of the stress required to separate two substrates bonded or adhered together. In certain embodiments, the higher the cure temperature, the less time required to achieve a desired cure level and / or bond strength. In certain embodiments, where near-ambient cure temperatures are employed, the adhesive composition can require more than 24 hours to achieve a desired cure level and / or bond strength.

[0096] Methods are also provided for using the adhesive compositions hereof. The adhesive composition can comprise any of the adhesive compositions described herein. The adhesive composition can be prepared using the method of formulating the adhesive composition described herein.

[0097] In certain embodiments, a method of using an adhesive composition hereof comprises applying the adhesive composition to a first substrate (to be adhered to a second substrate) andadhering the first substrate and the second substrate to each other such that the adhesive composition is sandwiched therebetween. Adhering the first and second substrates together can comprise placing the two substrates in physical contact and, optionally, applying a force or pressure such that the first and second substrates are pressed together.

[0098] The method further comprises curing the adhesive composition to chemically bond the substrates to the adhesive. In certain embodiments, for example where a substrate is porous or rough, the curing step can also result in mechanically bonding the rough or porous substrate to the cured adhesive.

[0099] The substrates (e g., first and second substrates) can comprise a variety of materials. The substrate can be selected from metal, wood, plastic such as polyvinyl chloride (PVC) or polytetrafluoroethylene (Teflon), ceramic, or any combination thereof. The substrate can be polished, sandblasted, or pre-scored or otherwise texturized to impart a texture thereon. One or more of the substrates can be a smooth substrate such as a metal (e.g., polished metal), a plastic, or a glass. One or more of the substrates can be a rough substrate such as, without limitation, a sandblasted metal or a texturized plastic. One or more of the substrates can be a porous substrate. One or more of the substrates can be flexible or rigid. A substrate can comprise glass, polycarbonate, polyimide, polysufone, carbon prepreg, aluminum, steel, iron, polyethylene terephthalate, cellulose (or paper), cross-ply prepreg carbon composite, plastic including, without limitation, acrylonitrile butadiene styrene, fabric, polyester film, and / or silicon.

[0100] The adhesive composition can be applied to substrates using a variety of methods, ranging from simple to more complex. In certain embodiments, the adhesive composition is scooped out of a mixing cup (or other container) using a tool (e.g. , a spatula) and deposited onto the top surface of a first substrate. In other cases, the adhesive composition is placed in a syringe and manually pressed through a needle. In other cases, the adhesive composition can be dispensed through a piston pump or similar device. In certain embodiments, the substrates have spacing elements sandwiched therebetween to prevent adhesive composition from being squeezed out from between the substrates to be bonded.

[0101] The adhesive composition can be applied to the substrate(s) in any pattern. In certain embodiments, the adhesive composition is applied as a layer to the first substrate. The adhesive composition can be deposited on the substrate in beads having a thickness of 60 to 1000 microns for example (noting, however, that any thickness of adhesive composition can be used as suitable for a particular application). The adhesive composition can be wet spread on the surface of the substrate (e.g, where the viscosity thereof allows).

[0102] The method can further comprise applying the adhesive composition to the second substrate in addition to the first substrate prior to adhering the first and second substrates together(e.g., such that the adhesive composition(s) are sandwiched between the first and second substrates).

[0103] Once applied, the adhesive composition can be cured. Curing can simply mean allowing the components of the adhesive composition to react over time to form bonds and cross-links therebetween. Curing can mean solvent removal and / or cross-linking within the adhesive composition such that the substrates to which the adhesive is applied remain in place. The curing process can be accelerated through the application of heat. In certain embodiments, heat is applied to the adhesive composition and substrate(s) to which the adhesive composition is applied. As noted above, in certain embodiments, increasing the temperature of an adhesive composition applied to a substrate will decrease the time required to achieve sufficient adhesive bonding and adhesion strength. In certain embodiments, the adhesive composition \\ i 11 automatically cure over a period of time, irrespective of the surrounding conditions (e.g., if ambient moisture is present or if one or both of the substrates comprise a solvent such as water).

[0104] Similar to the heating steps described above, the heating step can be performed using standard heating methodologies, such as application of a heat source to the adhesive composition. The heat source can be a an oven, a heat gun, a heatlamp (<?.g, an infrared heatlamp), a laser beam, or any other heat source suitable to apply heat to the adhesive composition applied to the substrate(s). In certain embodiments, the heat source is an electric heat source. In certain embodiments, the heat source is a hair dryer or other external heat source.

[0105] In certain embodiments, the heating / curing step can be performed under nitrogen atmosphere. In certain embodiments, the adhesive composition is not heated, but rather allowed to slowly cure at ambient or room temperature.

[0106] In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 50 °C to about 200 °C (such as about 50 °C to 200 °C, 50 °C to about 200 °C, or 50 °C to 200 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 65 °C to about 200 °C (such as about 65 °C to 200 °C. 65 °C to about 200 °C, or 65 °C to 200 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 70 °C to about 200 °C (such as about 70 °C to 200 °C, 70 °C to about 200 °C, or 70 °C to 200 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 100 °C to about 190 °C (such as about 100 °C to 190 °C, 100 °C to about 190 °C, or 100 °C to 190 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 120 °C to about 180 °C (such as about 120 °C to 180 °C, 120 °C to about 180 °C, or 120 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 135 °C to about 180 °C (such as about 135 °C to 180 °C, 135 °Cto about 180 °C, or 135 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 140 °C to about 180 °C (such as about 140 °C to 180 °C, 140 °C to about 180 °C, or 140 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 145 °C to about 180 °C (such as about 145 °C to 180 °C, 145 °C to about 180 °C, or 145 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 150 °C to about 180 °C (such as about 150 °C to 180 °C, 150 °C to about 180 °C, or 150 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 155 °C to about 180 °C (such as about 155 °C to 180 °C, 155 °C to about 180 °C, or 155 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 160 °C to about 180 °C (such as about 160 °C to 180 °C, 160 °C to about 180 °C, or 160 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 165 °C to about 180 °C (such as about 165 °C to 180 °C, 165 °C to about 180 °C, or 165 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 170 °C to about 180 °C (such as about 170 °C to 180 °C, 170 °C to about 180 °C, or 170 °C to 180 °C). In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 175 °C to about 180 °C (such as about 175 °C to 180 °C, 175 °C to about 180 °C, or 175 °C to 180 °C). The ranges specified herein are inclusive of the stated end points and specifically include all 1 °C increments within the specified ranges. In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about 50 °C to about 100 °C (such as about 50 °C to 100 °C, 50 °C to about 100 °C. or 50 °C to 100 °C) where the adhesive composition was prepared using a method comprising steps (i)-(iv) described herein and at least one of such steps (i)-(iv) included a heating step. In certain embodiments, the adhesive composition applied to the substrate(s) is heated to temperature of about about 155 °C to about 180 °C (such as about 155 °C to 180 °C, 155 °C to about 180 °C, or 155 °C to 180 °C) where the adhesive composition was prepared using a method comprising steps (i)-(iv) described herein and at least one of such steps (i)-(iv) included a heating step.

[0107] The adhesive composition applied to the substrate(s) can be heated to and maintained at the set temperature for about 0.5 hours to about 24 hours, such as about 0.5 hours to 24 hours, 0.5 hours to about 24 hours, or 0.5 hours to 24 hours (specified ranges inclusive of the stated end points and all 15 minute increments within the specified ranges). The adhesive composition, for example, can be maintained at the set temperature for about 24 hours. In certain embodiments, the mixture is heated to and maintained at a set temperature of about 180 °C, such as about 180 °C, for about 24 hours. The adhesive composition can be maintained at the set temperature for about8 hours to about 22 hours, such as about 8 hours to 22 hours, 8 hours to about 22 hours, or 8 hours to 22 hours. The adhesive composition can be maintained at the set temperature for about 10 hours to about 20 hours, such as about 10 hours to 20 hours, 10 hours to about 20 hours, or 10 hours to 20 hours. The adhesive composition can be maintained at the set temperature for about 12 hours to about 18 hours, such as about 12 hours to 18 hours, 12 hours to about 18 hours, or 12 hours to 18 hours. The adhesive composition can be maintained at the set temperature for about 14 hours to about 16 hours, such as about 14 hours to 16 hours, 14 hours to about 16 hours, or 14 hours to 16 hours. The adhesive composition can be maintained at the set temperature for at or about 24 hours. The ranges set forth in this paragraph are inclusive of the stated end points and all 30 minute increments within the specified ranges.

[0108] In certain embodiments, a vacuum can be applied to reduce any residual solvent that forms or is otherwise present in the adhesive composition.

[0109] In certain embodiments, the longer the time the adhesive composition is allowed to cure (z.e., maintained at the set temperature), the stronger the resulting adhesive bond with the substrate(s). In certain embodiments, the higher the temperature at which the adhesive composition is cured, the stronger the resulting adhesive bond with the substrate(s). For example, Fig. 3 show s the curing of certain embodiments of adhesives hereof placed betw een two pieces of steel and cured at 180 °C for 1, 3, 6, 18, or 24 hours. Bond strengths were significantly stronger at 180 °C than at either 70 °C or room temperature (Table 1). The 24-hour cure time provided the strongest bonds, although 6 hours of cure were close, generating a lower carbon footprint from heating.Table 1. shows the adhesion of sov-mal-tan to different substrates and cure conditions.

[0110] In certain embodiments, a method for simultaneously fonnulating and using an adhesive composition hereof is provided. There, one or more of the components of the adhesive composition are applied directly to the substrate(s). For example, the epoxidized oil, the phenolic compound(s), and / or the neutrophile(s) can be applied (e.g, as a pow der, liquid, mixture, and / orsolution) directly to the substrate(s) prior to any heating steps. In certain embodiments, one or more of the components of the adhesive composition can be applied to the first substrate, one or more components of the adhesive composition can be applied to the second substrate such that all adhesive composition components are mixed together upon adhering the first and second substrate together. The components of the adhesive composition can be applied sequentially or two or more can be pre-mixed with each other prior to application to the substrate(s). Thereafter, the adhesive composition deposited on the substrate(s) is cured as described above (<?.g, through the passage of time at ambient / room temperature, through the application of heat, and / or both) such that the adhesive composition forms covalent bonds and / or crosslinks, thus, adhering to the substrate(s).

[0111] Furthermore, the bonding characteristics of certain embodiments of the adhesives hereof were examined in connection with aluminum and steel substrates. Figs. 4A and 4B show that bonding was often well into structural strengths (e.g., > 1 MPa), ranging from 10 ± 1 MPa for sandblasted aluminum up to 16 ± 1 MPa for polished steel. The structural strengths for polished aluminum and sandblasted steel were about ~13 MPa. Adhesive controls containing only two components were substantially weaker or did not bond at all. Epoxidized soy oil with malic acid (no tannic acid) adhered at 1.9 ± 0.4 MPa. Malic acid with tannic acid (no epoxidized soy oil) formed a hard solid w ithout any ability to bond. Epoxidized soy oil and tannic acid (no malic acid) never cured to a solid.

[0112] The adhesive compositions hereof are capable of binding or adhering to a substrate even when the first substrate and / or the second substrate are exposed to dry, moist, wet, or underwater conditions. In certain embodiments, the adhesive composition can cure when applied in an aqueous environment or to a substrate that has previously been immersed in a liquid or that is presently immersed in a liquid (e.g., underwater conditions). A degree of water resistance is required to ensure that products remain intact when faced with difficult conditions. However, the water resistance of current industrial adhesives impedes debonding, recycling of components, and degradation in landfills. Water resistance studies were carried out to assess debonding of the adhesive. The water used for underwater environment testing was sea water. The substrates can be submerged underwater during the application of adhesive or after the application. Water resistance studies showed gradual debonding over the course when the substrate was submerged for a week. Fig. 10 shows that, when the substrate was submerged underwater for 24 hours, soy- mal-tan maintained -75-100% of initial dry bond strength. After one week underwater, -26-78% of the bonding persisted.

[0113] The adhesive composition can be used as a high-strength adhesive for automotive, construction, and electronic applications. The adhesive composition can be useful for adhering parts of a vehicle, wherein the vehicle can be automotive.

[0114] Lightweighting of automobiles and trucks can be an example of where the adhesive can provide additional environmental benefits. A change from heavy rivets and welds toward adhesive bonding can decrease vehicle weights and increase fuel efficiency. Fig. 10 shows how a pickup truck rocker panel could be riveted to sections of steel bars to represent a vehicle frame and shows soy-mal-tan adhesive performance for joining the substrates. The adhesive was cured with a heat gun for five minutes. By replacing 36.9 grams of steel rivets with 0.9 grams of glue, the bonding agent mass in these assemblies decreased by -97%.

[0115] Sustainability' goals for materials can include both having bio-based starting components as well as low levels of energy input. The soy-mal-tan was cured at 180 °C for 6 hours. For comparison, epoxies are cured using a wide range of conditions. It was observed that epoxies do not achieve a complete cure if only kept at room temperature. Automotive, construction, and electronic applications comprise a large percentage of epoxy consumption and common conditions may use 120-180 °C for 30 minutes.

[0116] A kit for preparing and / or using the adhesive compositions is also provided. In some embodiments, the kit comprises at least one of the adhesive compositions hereof and instructions for use. As used herein, ‘‘instructions for use” means a publication, a recording, a diagram, or any other medium of expression used to communicate the usefulness of the adhesive for one of the purposes set forth herein. The instructional material of the kit can, for example, be affixed to a container which contains the present adhesive composition and / or components thereof or be shipped together with a container which contains the adhesive composition and / or components thereof. Alternatively, the instructional material can be shipped separately from the container or provided on an electronically accessible form on an internet website with the intention that the instructional material and the adhesive composition be used cooperatively by the recipient.

[0117] In certain embodiments, the kit includes an epoxidized oil, a nucleophile (e.g., at least one nucleophile), a phenolic compound (e.g., at least one phenolic compound), and instructions for use. In certain embodiments, the kit further comprises a solvent. In certain embodiments, phenolic compound(s) is / are hydrated by the solvent for immediate use, such as in a syringe device or vial. In certain embodiments, the phenolic compound(s) and the nucleophile(s) are hydrated by the solvent for immediate use, with the epoxidized oil being housed apart therefrom (e.g. , in a separate syringe device or vial). In certain embodiments, the phenolic compound(s) and the nucleophile(s) are hydrated in the solvent for immediate use, such as in a dual syringe device to form a precursor liquid for addition to the epoxidized oil.

[0118] In certain embodiments, the kit comprises a pow dered form of the phenolic compound(s), the nucleophile(s), or both the the phenolic compound(s) and the nucleophile(s). Different components in pow dered form can be stored in a separate vial(s) or containers apart from the othercomponents of the adhesive composition. The solvent can be stored in a separate vial or container. The amounts of each of the components can be measured to achieve the desired ratios thereof and / or viscosity and / or properties of the adhesive composition or resultant adhesive (i.e., cured adhesive).

[0119] The kit can have a shelf life of about 18 months. As used herein, ‘"shelf life” is the length of time that the adhesive composition and / or components thereof can be stored without becoming unfit for use or sale and / or ineffective at exhibiting adhesive properties when cured. In certain embodiments, the kit has a shelf life of about 17 months. In certain embodiments, the kit has a shelf life of about 16 months. In certain embodiments, the kit has a shelf life of about 15 months. In certain embodiments, the kit has a shelf life of about 14 months. In certain embodiments, the kit has a shelf life of about 13 months. In certain embodiments, the kit has a shelf life of about 12 months. In certain embodiments, the kit has a shelf life of about 11 months.EXAMPLES Materials

[0120] Epoxidized soybean oil (ESO) 450 lb was purchased from the chemical company. DL- malic acid, fumaric acid, succinic acid, glycerol, tannic acid, gallic acid, and lignin were all purchased from Sigma- Aldrich and were used without modification. Pyrocatechol was purchased from Acros and used without modification.Example 1

[0121] Synthesis of epoxidized soy oil-malic acid-tannic acid (Soy-Mal-Tan)

[0122] 1.0 g of ESO was added to a 20 mL glass vial with a magnetic stir bar and heated at 70 °C in an oil bath. After sufficient heating to decrease viscosity, 1 mL of a 0.5 g / mL tannic acid / EtOH solution was added to the ESO and allowed to mix for ~5 minutes. 0.4 g of malic acid was then added slowly to the solution until dissolved fully. The reaction was heated overnight and taken out of the oil bath, and cooled to room temperature. At this point, the adhesive took on an amber color and was free-flowing while still warm and gradually hardened until at room temperature.Example 2

[0123] Synthesis of epoxidized soy oil-glycerol-tannic acid (Soy-Gly-Tan)

[0124] Soy-Gal-Tan was prepared using the procedure of Example 1 using epoxidized soy oil, glycerol, and tannic acid.

[0125] Preparation of Adherends

[0126] Metals. The steel used was low carbon and conforming to the ASTM A109 standard. Aluminum was of the 6061 alloy and conforming to the ASTM B209 standard.

[0127] Polished Substrates. Polished ASTM aluminum and stainless steel adherends (12 mm x 3.175 mm x 89 mm) were polished using various metal polishing bars and a polishing wheel. Stainless steel adherends were polished sequentially with a black emery bar and then a general green bar. Polished aluminum was prepared using only a brown tripoli bar due to the softness of aluminum. After polishing, excess grease was wiped away, and all substrates were cleaned using a progressive solvent system comprised of hexanes, acetone. MeOH, and finally, DI water. The substrates were allowed to dry overnight before use.

[0128] Sandblasted Substrates. ASTM aluminum and stainless steel adherends were placed in a sandblast cabinet and prepared using an abrasive comprised of fine glass bead media. The glass beads were used to create a rough surface on the substrates for a direct comparison of how soy- mal-tan performs on smooth or rough interfaces.

[0129] Low Energy Plastics. Polyvinyl chloride (PVC) and polytetrafluoroethylene (Teflon) substrates were cut into (12 mm x 12 mm x 89 mm) pieces. No special preparation for either material was necessary before use in adhesive testing

[0130] Wood. Pieces of pine were cut to 12 mm x 12 mm x 89 mm dimensions. Surfaces of pine substrates were treated briefly with 60 grit sandpaper.

[0131] Application of Adhesive on Substrates

[0132] 50 mg of soy-mal-tan was added to each lap shear pair of substrates. The material was applied while it was warm due to the viscosity providing ease of use. A second adherend was placed atop the first to form an overlap area of ~12 mm x ~12 mm. The lap-shear j oint was clamped together to allow the spreading of soy-mal-tan between the substrates. After cooling to room temperature, the material hardened between substrates. These joints were placed into an oven at 180 °C for 6 hours for the high-energy substrates and 24 hours with Teflon. The PVC samples were placed in an oven at a lower temperature, 110 °C, for 24 hours, owing to the melting point of this plastic. After curing at 180 °C, soy-mal-tan appeared dark brown / black in color and was harder than after the initial reaction.

[0133] Adhesion Testing

[0134] Adhesive strength was initially determined using an Instron 5544 fitted with a 2 kN load cell. Samples that would breach the load cell capacity were measured on an MTS Insight materials testing instrument with a 10 kN load cell or an Instron 34TM-30 instrument with a 30 kN load cell. Samples for both the Instron and MTS were placed in the instrument using two steel crossbars (e.g., drill bit blanks) to hold each adherend in place. The crossbars were pulled apart to stress thejoints at a pull rate of 2 mm / min. The maximum force applied on the joints prior to failure was recorded in Newtons (N). The resulting adhesive strength in units of megapascals (MPa) was calculated by dividing this maximum force (N) by the joint overlap area (m2). Adhesion data reported are averages from a minimum of 10 samples, with error bars representing 90% confidence intervals. One exception here was n = 5 for water resistance testing of EMT. In cases where a joint fell apart as soon as it was picked up, these samples were given a value of zero when calculated into averages.

[0135] Artificial Sea Water

[0136] Aquacraft Marine Environment Salt mixture was used to make artificial sea water. The salts were dissolved into reverse osmosis purified water to a final salinity of 28-30 ppt measured by a refractometer. The water was aerated for at least seven days prior to use.

[0137] Characterization

[0138] IR Spectroscopy. Infrared spectra w ere obtained using a Thermo Nicolet Nexus FT-IR with a Diamond and ZnSe ATR. Data from solid samples were collected from 800-4500 cm’1using an MCT detector. These data were analyzed to determine the disappearance of functional groups.

[0139] Infrared (IR) spectroscopy suggested similar bonding schemes with a potential acid-to- ester shift (-1680 to -1720 cm’1) upon the reaction of malic acid with epoxidized soy oil in both the presence and absence of tannic acid (Fig. 9). The carboxylic acid CO-OH bands of malic acid (1408, 1278 cm’1) were also less observable after combination with epoxidized soy oil.

[0140] NMR Spectroscopy. Samples for the NMR study were prepared using DMSO-t / 6 solvent and ran using an Oxford 300 MHz magnet. H-NMR andnC-NMR were performed for each sample and subsequently analyzed using Mestrenova software. Peaks were isolated for individual spectra to observe the appearance or disappearance of specific groups.

[0141] According to proton nuclear magnetic resonance (1H NMR) spectroscopy, the starting epoxy groups in epoxidized soy oil disappeared upon reaction with malic acid or, to a lesser degree, with tannic acid (Fig. 9). Consumption of epoxy groups upon reaction with both malic and tannic acids was further confirmed by acid titration. Also seen in the1H NMR spectra was the appearance of an alcohol (3.38 ppm), a characteristic result of an epoxy ring opening after a reaction with a nucleophile. The 'l l NMR alcohol resonance of malic acid never changed, indicating that acid groups were the ones from malic acid reacting with the epoxies. Observing small shifts in the13C NMR spectra indicative of aliphatic ester formation with epoxidized soil oil + malic acid + tannic acid (-172.2 ppm) or epoxidized soil oil + malic acid (-172.5 ppm) (Fig. 9B) supported acid + epoxy coupling. The presence of multiple broad peaks indicates the formation of a system that is cross-linked and heterogeneous.

[0142] Differential scanning calorimetry (DSC). Differential scanning calorimetry was performed using a Perkin Elmer with a 2P Intracooler and nitrogen gas purge. Each scan was programmed to run from -10 to 200 °C at 10 °C / min and cooled from 200 to -10 °C at 40 °C / min. The individual thermograms were used to calculate the glass transition temperature of each material.

[0143] DSC showed that thermal events for epoxidized soy oil. an oil at room temperature, could be shifted to higher temperatures upon reaction with malic acid and, possibly, tannic acid. For the complete system of epoxidized soil oil + malic acid + tannic acid, a unique high-temperature thermal event was present that did not correlate to epoxidized soil oil (below room temperature), tannic acid (> 200 °C alone), or malic acid.

[0144] Epoxy Titration. Determining the epoxy groups remaining after the reaction was performed using a previously published ASTM method. Samples were titrated from a stock HBr solution until the color changed to the same as a control. Volumes to reach color change were used to calculate epoxy concentration.

[0145] Temperatures. A standard Type T thermocouple was used to determine the approximate output temperatures of a household hair drier and laboratory' heat gun.

[0146] Microscopy. Scanning electron microscopy images were collected using an FEI Quanta 3D FEG instrument with a gallium ion beam, Everhart-Thornley detector, and a typical accelerating voltage of 5 kV.

[0147] When bonded joints were pulled apart and examined by scanning electron microscopy (SEM, Fig.7). A mixture of adhesive and cohesive failure mechanisms was found in both epoxy and soy-mal-tan samples, although differences were apparent. The epoxy showed a single, clean fracture, typical of brittleness. The SEM image of soy-mal-tan was more complex, with several stress lines providing evidence for distribution of mechanical forces throughout the bulk material. Here, too, soy-mal-tan appears to be less brittle than the epoxy.

[0148] Analogous data for the soy-mal-tan adhesive cured at room temperature, 70 °C, and 180 °C displayed somewhat gradual failure, indicative of materials that are more ductile than the brittle commercial counterparts. A similar story was seen when bonded joints were pulled apart and examined by scanning electron microscopy (SEM, Fig.7). A mixture of adhesive and cohesive failure mechanisms was found in both epoxy and soy-mal-tan samples, although differences were apparent. The epoxy showed a single, clean fracture, typical of brittleness. The SEM image of soy-mal-tan was more complex, with several stress lines providing evidence for the distribution of mechanical forces throughout the bulk material. Soy-mal-tan appeared to be less brittle than epoxy.

[0149] These analytical methods indicate that soy-mal-tan is an extensively cross-linked matrix with all three components participating in covalent bond formation. Epoxidized soy oil and malicacid coupled together via aliphatic ester bonds. Malic acid also reacted directly with tannic acid via aromatic ester bonds. Perhaps less prominent are esters formed comprised of tannic acid coupled to epoxidized soy oil.

[0150] Lap shear testing. The adhesive composition was placed between two pieces of steel and cured at 180 °C for 3, 18. or 24 hours. The 24-hour cure time provided the most promising results. After cooling, joints were pulled to failure, and adhesion was quantified in maximum force at failure divided by the substrate overlap area.

[0151] Lap shear bonding provides a practical means of obtaining large volumes of data with high reproducibility. Joints were pulled apart, and adhesion was quantified by maximum force at failure divided by the substrate overlap area. Different ratios of components were examined for epoxidized soy oil and tannic acid with either glycerol or malic acid (Figs. 1 and 2). In the end, the highest-strength system was a 1:0.4:0 5 mass ratio of epoxidized soy oil: malic acid: tannic acid (“soy-mal-tan”). Each gram of soy-mal-tan contained ~ 0.4 grams of ethanol in order to solubilize the tannic acid.

[0152] Bonding strengths. To quantify the performance of soy-mal-tan, bonding was examined with aluminum and steel, each polished or sandblasted. Fig. 4A and 4B show that this new adhesive system bonded well into structural strengths at 10± MPa with each substrate for sanded aluminum up to 16 ± 1 MPa for polished steel. Both polished aluminum and sandblasted steel were in between at -13 MPa. Controls of only two components were substantially weaker or did not bond at all. Epoxidized soy oil with malic acid (no tannic acid) adhered at 1.9 ± 0.4 MPa. Malic acid with tannic acid (no epoxidized soy oil) formed a hard solid without any ability to bond. Epoxidized soy oil and tannic acid (no malic acid) never cured to a solid.

[0153] Benchmarking against commercial products is also shown in Fig. 6. Each glue was cured according to instructions from the manufacturer (e g., time, temperature, use of clamps) and applied in the same quantity (~ 50 mg) between substrates as soy-mal-tan. Two of the most widely available bio-based adhesives are starch glue and hide glue. Fig. 6A with sandblasted steel substrates shows that the bio-based products bonded at ~0.7- 1.5 MPa, about an order of magnitude less than soy-mal-tan. Amongst the petroleum-derived products, Elmer’s Glue- All (a polyvinyl acetate) and Gorilla Glue (a polyurethane) were also weak with sandblasted steel at -1.0-1.2 MPa. The bonding here of Super Glue (a cyanoacry late, 10 ± 2 MPa) and epoxy (13 ± 2 MPa) were similar to that of soy-mal-tan (13 ± 2 MPa). When used on polished aluminum substrates, soy- mal-tan (13 ± 1 MPa) exceeded the performance of all benchmarks including Super Glue (9 ± 4 MPa) and epoxy (7 ±1 MPa), which is generally considered to be the strongest type of structural adhesive 1, 2 (Fig. 6B). Fig. 6C shows data for an example low surface energy7substrate, polytetrafluoroethylene (Teflon). Here the petroleum-based glues were strongest (-0.7 - 1 MPa),whereas soy-mal-tan (0.3 ± 0.1 MPa) outperformed the commercial bio-based products (-0-0.05 MPa). Analogous adhesion data for polished steel, sandblasted aluminum, and polyvinyl chloride (PVC) substrates are also provided in Figs. 4A, 4B, and 5.

[0154] Wood is particularly sustainable, with plywood being one of the most widely used construction materials. Reaction (70 °C. five days) and cure (120 °C, three days) conditions were changed for wood. Both soy-mal-tan and most commercial systems achieved bonds exceeding the strength of wood (Fig. 6D). Intact adhesive j oints and broken wood can be seen in Fig. 6E. Although the conditions used to bond wood were somewhat extreme, the observation of substrate failure indicated that less harsh parameters may be relevant to real-world use.

[0155] To explore a range of potential use conditions, soy-mal-tan (1:0.4:0.5 ratio) was applied between polished steel substrates with a room temperature cure of 24 hours. The bond strength, at 0.7 ± 0.1 MPa, w as lower than that from a 180 °C cure at 6 hours (16 ± 1 MPa). An alternative cure using a household hair dryer (~ 65 °C) for 5 minutes may have increased the bonding to 1.2 ± 0.5 MPa. A higher temperature laboratory heat gun (-200 °C) for 5 minutes generated 4. 1 ± 0.4 MPa. Table 1 (above) shows similar data for polished aluminum, sandblasted aluminum, and sandblasted steel.

[0156] A degree of water resistance is required to ensure that products remain intact w hen faced with difficult conditions. However, the water resistance of current industrial adhesives impedes debonding, recycling of components, and degradation in landfills. The water resistance of the adhesive was tested. Bonded pairs of polished aluminum substrates were subjected to harsher conditions than many consumer products will experience. Joints with 1.2 x 1.2 cm overlap were cured in the air (70 °C, 24 hours or 180 °C, 6 hours) and then submerged under deionized water for varying times, followed by measuring of bond strengths. Fig. 10 shows that, when underwater for 24 hours, soy-mal-tan maintained -75-100% of initial, dry bond strength. Even after one week underwater, -26-78% of the bonding persisted. Analogous experiments were carried out in artificial sea water and showed generally similar results, although with slightly more rapid losses of bonding over time (Fig. 10). These extremes of deionized to artificial sea waters span most aqueous conditions and indicate the potential role of salt in debonding to be minor.

[0157] A control experiment showed that the performance of epoxy w as also influenced by salt water. Over the course of a week underwater, the average strengths of joints did not change significantly; however, error bars increased dramatically. Epoxies are known to swell in water. Here water exposure made the epoxy more flexible, and bubbles began to form, indicating that water was entering the material. Polished aluminum substrates, bonded together with soy-mal-tan and cured at 180 °C for 24 hours, were subjected to harsh conditions of submersion into boilingdeionized water for 4 hours (Fig. 11). Adhesion of these samples was at 3 ± 2 MPa, compared to 15 ± 1 MPa for control samples left on a benchtop.

[0158] Industrial strength needs for adhesive performance span a wide range with, for example, packaging being not particularly challenging at 0.5-4 MPa. At the other extreme are the high requirements of automotive and aerospace structures at 5-30 MPa. Making direct numerical comparisons can be tricky, with variables including changes to joint configurations, substrates, environments, and use conditions. Nonetheless, soy-mal tan bonded metals at -10-16 MPa and are potentially within the needs of the most demanding applications.

[0159] Lightweighting of automobiles and trucks is an example of where new materials may provide additional environmental benefits. A change from heavy rivets and welds toward adhesive bonding can decrease vehicle weights and increase fuel efficiency. Fig. 4B shows how a pickup truck rocker panel could be riveted to sections of steel bars to represent a vehicle frame. Also shown is an alternative using soy-mal-tan for joining the substrates. Here the adhesive was cured with a heat gun for five minutes. By replacing 36.9 grams of steel rivets with 0.9 grams of glue, the bonding agent mass in these assemblies decreased by - 97%.

[0160] CO2 emission data. Producing and curing one ton of epoxy was estimated to generate - 5.8 tons of CO2 emissions. Production of one ton of soy-mal-tan consumed - 11 tons of CO2, and curing of one ton of soy-mal-tan emitted - 6.6 tons of CO2. Thus, the estimated production and use for one ton of soy-mal-tan may absorb roughly 4.4 tons of CO2.

[0161] In addition, any of the embodiments described in the following clause list are considered to be part of the invention.A. An adhesive composition comprising (1) an epoxidized oil (EO), (li) at least one nucleophile, and (iii) at least one phenolic compound.B. The adhesive composition of clause A, wherein the epoxidized oil is epoxidized soy oil.C. The adhesive composition of clause A, wherein the at least one nucleophile is a compound comprising a moiety selected from the group consisting of an acid, an alcohol, an amine, and a thiol.D. The adhesive composition of clause C, wherein the at least one nucleophile is selected from fumaric acid, glycerol, malic acid, succinic acid, or a combination thereof.E. The adhesive composition of clause D, wherein the at least one nucleophile is malic acid.F. The adhesive composition of clause A, wherein the at least one phenolic compound is selected from catechol, gallic acid, gallol. lignin, tannic acid, or a combination thereof.G. The adhesive composition of clause F, wherein the at least one phenolic compound is tannic acid.H. The adhesive composition of clause A or G, wherein the composition further comprises a solvent.I. The adhesive composition of clause A. wherein the composition further comprises a solvent selected from alcohol, water, chlorofonn, dichloromethane, dimethyl sulfoxide, and dimethyl formamide.J. The adhesive composition of clause I, wherein the solvent is ethanol or methanol.K. The adhesive composition of any one of clauses A-G, I, or J, wherein the EO, the nucleophile(s), and the phenolic compound(s) are present in a mass ratio from about 1 :0.1 :0.1 to about 1: 10: 10, respectively.L. An adhesive composition consisting essentially of (i) an epoxidized soy oil (ESO), (ii) malic acid, (iii) tannic acid, and (iv) ethanol.M. The adhesive composition of clause L, wherein the ESO, malic acid, and tannic acid are present in a mass ratio from about 1: 0.1 : 0.1 to about 1 : 10: 10, respectively.N. An adhered substrate comprising a substrate comprising the adhesive composition of any one of clause A-M applied thereto.O. The adhered substrate of clause N, wherein the substrate is exposed to dry, wet, moist, or underwater conditions.P. The adhered substrate of clause O, wherein the substrate comprises metal, wood, plastic, ceramic, or any combination thereof.Q. The adhered substrate of clause P, wherein the metal substrate is steel or aluminum.R. A method of manufacturing the adhesive composition of clause A or L, which method comprises: mixing a phenolic compound with an epoxidized oil (EO) to obtain an EO solution or mixture, wherein the phenolic compound is optionally in the form of a solution in a solvent; adding a nucleophile to the EO solution or mixture and heating said resulting reaction mixture; and cooling the reaction mixture to room temperature, whereupon the adhesive composition is obtained.S. The method of clause R, wherein the EO is epoxidized soy oil.T. The method of clause R. further comprising heating the EO prior to mixing the phenolic compound therewith, wherein the EO and reaction mixture are heated at a temperature of about 70° C to about 90 °C.U. The method of clause R, wherein the solvent is selected from alcohol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide.V. The method of clause R, wherein the nucleophile is a compound comprising a moiety selected from the group consisting of an acid, an alcohol, an amine, and a thiol.W. The method of clause V, wherein the nucleophile is selected from fumaric acid, glycerol, malic acid, succinic acid, or a combination thereof.X. The method of clause W, wherein the nucleophile is malic acid.Y. The method of clause R, wherein the phenolic compound is selected from catechol, gallic acid, gallol, lignin, tannic acid, or a combination thereof.Z. The method of clause Y, wherein the phenolic compound is tannic acid.A’. A method of using the adhesive composition of any one of clause A-M, which method comprises applying the adhesive composition to at least a first substrate, which is to be adhered to at least a second substrate, and adhering the at least first substrate and the at least second substrate to each other.B’. The method of clause A', which further comprises applying the adhesive composition to the at least second substrate prior to adhering the at least first substrate and the at least second substrate.C’. The method of clause A’ or B’, wherein the at least first substrate and / or the at least second substrate are exposed to dry, moist, wet, or underwater conditions.D’. The method of clause A’ or B’, wherein the at least first substrate and / or the at least second substrate comprises metal, wood, plastic, ceramic, or any combination thereof.E’. The method of clause D’, wherein the metal is steel or aluminum.

[0162] As used herein, the following terms and phrases shall have the meanings set forth below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art.

[0163] The term '‘about / ’ when referring to a number or a numerical value or range (including, for example, whole numbers, fractions, and percentages), means that the number or numerical range referred to is an approximation within experimental variability (or within statistical experimental error) and thus the numerical value or range can vary between 1% and 10% of the stated number or numerical range (e.g, + / - 5 % to 10% of the recited value) provided that one of ordinary skill in the art would consider equivalent to the recited value (e.g, having the same function or result). The term “substantially” can allow7for a degree of variability’ in a value or range, for example, within 90%, within 95%, 99%, 99.5%, 99.9%, 99.99%, or 99.999% or more of a stated value or of a stated limit of a range, inclusive of the specified end points.

[0164] The term "substantially" can allow for a degree of variability in a value or range, for example, within 90%, within 95%, or within 99% of a stated value or of a stated limit of a range.

[0165] The terms "a," "an," or "the" are used to include one or more than one unless the context clearly dictates otherwise. The term "or" is used to refer to a nonexclusive "or" unless otherwiseindicated. In addition, the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid the reading of the document and is not to be interpreted as limiting. Further, information that is relevant to a section heading may occur within or outside of that particular section. The terms "including" and "having" are defined as comprising (i.e., open language).

[0166] Furthermore, all publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated references should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0167] Those skilled in the art will recognize that numerous modifications can be made to the specific implementations described above. The implementations should not be limited to the particular limitations described. Other implementations may be possible.

[0168] It is intended that the scope of the present methods and apparatuses be defined by the following claims. However, it must be understood that this disclosure may be practiced otherwise than is specifically explained and illustrated without departing from its spirit or scope. It should be understood by those skilled in the art that various alternatives to the embodiments described herein may be employed in practicing the claims without departing from the spirit and scope as defined in the following claims.

Claims

WE CLAIM:

1. An adhesive composition comprising (i) an epoxidized oil (EO), (ii) at least one nucleophile, and (iii) at least one phenolic compound.

2. The adhesive composition of claim 1, wherein the epoxidized oil is epoxidized soy oil.

3. The adhesive composition of claim 1, wherein the at least one nucleophile is a compound comprising a moiety’ selected from the group consisting of an acid, an alcohol, an amine, and a thiol.

4. The adhesive composition of claim 3, wherein the at least one nucleophile is selected from fumaric acid, glycerol, malic acid, succinic acid, or a combination thereof.

5. The adhesive composition of claim 4, wherein the at least one nucleophile is malic acid.

6. The adhesive composition of claim 1, wherein the at least one phenolic compound is selected from catechol, gallic acid, gallol, lignin, tannic acid, or a combination thereof.

7. The adhesive composition of claim 6, wherein the at least one phenolic compound is tannic acid.

8. The adhesive composition of claim 1 or 7, wherein the composition further comprises a solvent.

9. The adhesive composition of claim 1 , wherein the composition further comprises a solvent selected from alcohol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide.

10. The adhesive composition of claim 9. wherein the solvent is ethanol or methanol.

11. The adhesive composition of any one of claims 1 -7, 9, or 10, wherein the EO, the at least one nucleophile, and the at least one phenolic compound are present in a mass ratio from about 1:

0. 1:0.1 to about 1: 10: 10, respectively.

12. An adhesive composition consisting essentially of (i) an epoxidized soy oil (ESO), (ii) malic acid, (iii) tannic acid, and (iv) ethanol.

13. The adhesive composition of claim 12, wherein the ESO, malic acid, and tannic acid are present in a mass ratio from about EO. EO. l to about 1: 10: 10, respectively.

14. An adhered substrate comprising a substrate comprising the adhesive composition of any one of claims 1-13 applied thereto.

15. The adhered substrate of claim 14, wherein the substrate is exposed to dry, wet, moist, or underwater conditions.

16. The adhered substrate of claim 14, wherein the substrate comprises metal, wood, plastic, ceramic, or any combination thereof.

17. The adhered substrate of claim 16, wherein the metal substrate is steel or aluminum.

18. A method of manufacturing the adhesive composition of claim 1 or 12, which method comprises: mixing a phenolic compound with an epoxidized oil (EO) to obtain an EO solution or mixture, wherein the phenolic compound is optionally in the form of a solution in a solvent; adding a nucleophile to the EO solution or mixture and heating said resulting reaction mixture; and cooling the reaction mixture to room temperature, whereuopn the adhesive composition is obtained.

19. The method of claim 18, wherein the EO is epoxidized soy oil.

20. The method of claim 18, wherein the EO is optionally heated prior to mixing the phoenolic compound therewith, and the EO and reaction mixture are heated or maintained at a temperature of about 70° C to about 90 °C.

21. The method of claim 18, wherein the solvent is selected from alcohol, water, chloroform, dichloromethane, dimethyl sulfoxide, and dimethyl formamide.

22. The method of claim 18, wherein the nucleophile is a compound comprising a moiety selected from the group consisting of an acid, an alcohol, an amine, and a thiol.

23. The method of claim 22, wherein the nucleophile is selected from fumaric acid, glycerol, malic acid, succinic acid, or a combination thereof.

24. The method of claim 23, wherein the nucleophile is malic acid.

25. The method of claim 18, wherein the phenolic compound is selected from catechol, gallic acid, gallol, lignin, tannic acid, or a combination thereof.

26. The method of claim 25, wherein the phenolic compound is tannic acid.

27. A method of using an adhesive composition, which method comprises applying the adhesive composition of any one of claims 1-13 to at least a first substrate, which is to be adhered to at least a second substrate, and adhering the first substrate and the second substrate to each other such that the adhesive composition is sandwiched therebetween.

28. The method of claim 27, which further comprises applying the adhesive composition to the second substrate prior to adhering the first substrate and the second substrate.

29. The method of claim 27 or 28, wherein the first substrate and / or the second substrate are exposed to dry. moist, wet, or underwater conditions.

30. The method of claim 27 or 28, wherein the first substrate and / or the second substrate comprises metal, wood, plastic, ceramic, or any combination thereof.

31. The method of claim 30, wherein the metal is steel or aluminum.

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