BIO-based adhesive system

Abstract

A two-component adhesive system and methods of making and using the same. The adhesive system contains a component (A): a hydroxyl-containing compound and an organic acid amine complex or an aliphatic polyester diaol and a component (B): an aliphatic isocyanate and / or a cycloaliphatic isocyanate. The adhesive composition of the present invention is water-based and has low or is free from volatile organic compounds ("VOC"). The adhesive composition also may be composed of one or more bio-based material totaling from 24% to 95% and may have high solids of over 60% after component A and B are mixed.

Description

[0001] Attorney Docket 40787 / 41 BIOB-002 / 01WO TITLE OF THE INVENTION BIO-BASED ADHESIVE SYSTEM CROSS-REFERENCE TO RELATED APPLICATIONS The present application claims priority to U.S. Prov. Appl. No.63 / 641,768, filed May 2, 2024, the entire contents of which is incorporated herein by reference. FIELD OF THE INVENTION The present invention provides a two-component adhesive system and methods of making and using the same. The adhesive system contains a component (A): a hydroxyl- containing compound and an organic acid amine complex or an aliphatic polyester diol and a component (B): an aliphatic isocyanate and / or a cycloaliphatic isocyanate. The adhesive composition of the present invention is water and biobased and has low or is free from volatile organic compounds (“VOC”). The adhesive composition also may be composed of one or more bio-based material totaling from 24% to 95% and may have high solids of over 60% after component A and B are mixed. DISCUSSION OF THE BACKGROUND Every day people are surrounded by and exposed to toxic glues and coatings. Conventional polyurethane based adhesive systems may be formed by reacting an isocyanate compound with a polyol compound, of which the polyol used may have at least one petroleum-based building block (such as ethylene oxide and / or propylene oxide). While such petrochemical based polyols are widely used, these polyols face many problems in addition to the health drawbacks, such as exhaustion of natural resources and fluctuations in price based on changes in oil price. Although bio-based oils may seem to be an attractive alternative, Attorney Docket 40787 / 41 BIOB-002 / 01WO most bio-based oils are not miscible in water and therefore these alternatives typically contain volatile organic compounds and / or strong off-gassing odors. In view of the foregoing, there remains a critical need in the art to develop safe and effective adhesives. SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-based two-component adhesive system that provides having excellent adhesion, excellent durability, and excellent corrosion, chemical and acid resistance, while having low or no VOCs or odor and is easy to apply, dries at ambient temperatures within 8 hours or less and easy to clean up with water. The adhesive system contains a component (A): a hydroxyl-containing compound and an organic acid amine complex or an aliphatic polyester diol and a component (B): an aliphatic isocyanate and / or a cycloaliphatic isocyanate. The adhesive composition of the present invention is water-based and has low or is free from volatile organic compounds (“VOC”). The adhesive composition also may be composed of one or more bio-based material totaling from 24% to 95% and may have high solids of over 60% after component A and B are mixed. A kit containing, separately packaged component (A) and component (B) together with instructions for use thereof, wherein component (A) comprises a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate, and wherein component (A) and component (B) are water-based and have low or are free from volatile organic compounds. A method of making an adhesive composition, by Attorney Docket 40787 / 41 BIOB-002 / 01WO (1) Stirring, shaking, or agitating a component (A) comprising a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol for a time and under conditions to fully disperse the hydroxyl-containing compound and organic acid amine complex and / or an aliphatic polyester diol; (2) Stirring, shaking, or agitating a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate for a time and under conditions to fully disperse the aliphatic isocyanate and / or a cycloaliphatic isocyanate; and (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form an adhesive composition. A method of adhering a surface of a first material to a surface of second material, comprising: (1) applying a layer of an adhesive composition prepared by the foregoing method to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles); (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to cure. A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises the reaction product of a component (A) comprising a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol and a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, wherein the adhesive contains low or no VOCs and has at least 24 wt% of a bio-based material (e.g., a plant-based and / or bio-renewable polymer). Attorney Docket 40787 / 41 BIOB-002 / 01WO The above objects highlight certain aspects of the invention. Additional objects, aspects and embodiments of the invention are found in the following detailed description of the invention. BRIEF DESCRIPTION OF THE FIGURES The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following Figures in conjunction with the detailed description below. Fig.1 shows a wood sample adhered using an adhesive composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION Unless specifically defined, all technical and scientific terms used herein have the same meaning as commonly understood by a skilled artisan in chemistry (e.g., polyurethane chemistry), coatings, and adhesives. All methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, with suitable methods and materials being described herein. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. Further, the materials, methods, and examples are illustrative only and are not intended to be limiting, unless otherwise specified. Attorney Docket 40787 / 41 BIOB-002 / 01WO Reference will now be made in detail to each embodiment of the present invention. Such embodiments are provided by way of explanation of the present invention, which is not intended to be limited thereto. In fact, those of ordinary skill in the art may appreciate upon reading the present specification and viewing the present drawings that various modifications and variations can be made thereto. Component (A) Component (A) contains a hydroxyl-containing compound and (i) an organic acid amine complex and / or (ii) an aliphatic polyester diol. In an embodiment, component (A) has low VOC content or is free from (i.e., has zero) VOCs. As low VOC content, it is envisioned that there is less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.05 wt%, less than 0.01 wt% total VOCs. In an embodiment, component (A) is water-based (i.e., is contained in water as a solvent). In an embodiment, component (A) is free from organic solvents. In an embodiment, the hydroxyl-containing compound is a plant-based compound comprising hydroxyl groups. In an embodiment, the plant-based compound comprising hydroxyl groups is a cardanol compound. Cardanol provides several advantages including fast curing, low temperature, adhesion, surfactant effect, thermal and fire resistance, chemical resistance, water resistance, flexibility, low viscosity, surface tension, and wetting properties. Cardanol has a general structure of formula (I): Attorney Docket 40787 / 41 BIOB-002 / 01WO wherein R1is —C15H25, —C15H27, —C15H29,or —C15H31. Specific examples of R1include: It is understood that within the scope of the present invention the cardanol compound may be a blend of one of more of the foregoing compounds of formula (I). Exemplary cardanol compounds include cardanol compounds of formulae (II) – (V):

[0002] Attorney Docket 40787 / 41 BIOB-002 / 01WO In an embodiment of the present invention, of the cardanol compounds present, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97.5 wt%, at least 99 wt%, or about 100 wt% is tri-unsaturated cardanol (-C15H25;formula (II)). Alternatively, of the cardanol compounds present, 25 to 65 wt%, 30 to 60 wt%, 35 to 55 wt%, or 40 to 50 wt% is tri-unsaturated cardanol (-C15H25; formula (II)). Attorney Docket 40787 / 41 BIOB-002 / 01WO In an embodiment of the present invention, of the cardanol compounds present, 15 to 50 wt%, 20 to 45 wt%, 25 to 40 wt%, or 30 to 35 wt% is mono-unsaturated (-C15H29;formula (IV)). In an embodiment of the present invention, of the cardanol compounds present, 5 to 40 wt%, 10 to 35 wt%, 15 to 30 wt%, or 20 to 25 wt% is bi-unsaturated (-C15H27;formula (III)). In an embodiment of the present invention, of the cardanol compounds present, 0 to 10 wt%, 0.5 to 7.5 wt%, 1 to 5 wt%, 2 to 4 wt% is saturated (-C15H31;formula (V)). An exemplary formulation of cardanol compounds for use in the present invention includes: tri-unsaturated cardanol (-C15H25;formula (II)), the major component is present at from 35 to 55 wt%, from 25 to 40 wt% mono-unsaturated cardanol (-C15H29; formula (IV)), from 15 to 30 wt% bi-unsaturated cardanol (-C15H27;formula (III)), and 1 to 5% saturated cardanol (-C15H31;formula (V)). A specific exemplary formulation of cardanol compounds for use in the present invention includes: tri-unsaturated cardanol (-C15H25;formula (II)), the major component (41%). The remaining cardanol is 34% mono-unsaturated (-C15H29; formula (IV)), 22% bi- unsaturated (-C15H27;formula (III)), and 2% saturated (-C15H31;formula (V)). The cardanol compound may be a by-product of cashew nut processing (e.g., may be extracted from a layer between a nut and a shell of a cashew nut). Within the present invention, the cardanol compound may be used in the form of cashew nutshell liquid. Component (A) may further contain cardol, methylcardol, and / or anacardic acid as secondary components. Cardol has the general structure of formula (VI): Attorney Docket 40787 / 41 BIOB-002 / 01WO R1is as defined above. Methylcardol has the general structure of formula (VII): R1is as defined above. Anacardic acid has the general structure of formula (VIII): (VIII): R1is as defined above. In an embodiment, component (A) may include at least 50 wt % (e.g., at least 60 wt %, at least 70 wt %, at least 80 wt %, at least 90 wt %, and / or 100 wt %) of cardanol. Component (A) may include cardanol as a primary component and may additionally include cardol, methylcardol, and / or anacardic acid as secondary components. For example, component (A) may include at least 50 wt % (e.g., at least 60 wt %, at least 70 wt %, at least 80 wt %, at least 90 wt %, and / or 100 wt %) of cardanol; from 20 wt % to 50 wt % (e.g., from 20 wt % to 45 wt %, from 25 wt % to 40 wt %, from 35 wt % to 40 wt %, etc.) of cardol; and Attorney Docket 40787 / 41 BIOB-002 / 01WO the remainder based on a total of 100 wt % of component (A) being methylcardol and / or anacardic acid. According to an exemplary embodiment, component (A) includes at least 50 wt % of cardanol and at least 35 wt % of cardol with the remainder based on a total of 100 wt % of component (A) being methylcardol and / or anacardic acid. Component (A) may be subjected to a heating process (e.g., at the time of extraction from the cashew nut), a decarboxylation process, and / or a distillation process. According to an exemplary embodiment, component (A) is a decarboxylated cashew nutshell liquid that includes at least 50 wt % of cardanol and at least 35 wt % of cardol. Without intending to be bound by this theory, component (A) may increase hydrophobicity, reduce viscosity, increase gel time of the polyurethane resin, and / or provide tensile strength. Other potential bio-based components that may be used as a hydroxyl-containing compound in component (A) include soy, zein, castor, grapeseed oil, seaweed oil, jojoba oil, avocado oil and other plant-based oils. In an embodiment, component (A) includes one or more isolated product from soy, zein, castor, grapeseed oil, seaweed oil, jojoba oil, avocado oil and other plant-based oils. For example, instead of using raw castor oil component (A) may contain ricinoleic acid and / or a triester of glycerol and ricinoleic acid. In addition, it is envisioned that with the present invention one or more of the aforementioned bio-based materials (e.g., soy, zein, castor, grapeseed oil, seaweed oil, jojoba oil, avocado oil and other plant-based oils) or a component isolated therefrom may be derivatized to add a hydroxyl functionality or to increase to increase the hydroxyl count. In an embodiment, the organic amine complex is of any well-known type. By way of example, reference is made to U.S. Patent No.5,519,074 (incorporated herein by reference), which describes complexes of morpholine derivatives with amine salts of keto-acids. An exemplary organic amine complex is HALOX 570 (manufactured by ICL / Halox). The Attorney Docket 40787 / 41 BIOB-002 / 01WO presence of the organic amine complex serves as a corrosion inhibitor, but also increases the adhesion including direct to metal and the viscosity of component (A). An aliphatic polyester diol for use in the present invention may be any linear or lightly branched polymer that contains repeating ester (–COO–) linkages in its backbone, terminates in two hydroxyl (–OH) groups, and is made entirely or primarily from aliphatic (non-aromatic) monomers. Exemplary aliphatic polyester diols include Poly(1,4-butanediol adipate) (PBA or PBAD), Poly(1,6-hexanediol adipate) (PHA), Polycaprolactone diol (PCL diol), Poly(diethylene glycol adipate), Poly(ethylene adipate) (PEA), Poly(1,3-propanediol sebacate), Poly(1,4-butanediol succinate) (PBDS), Poly(neopentyl glycol adipate) (NPG- Adipate), Poly(hexanediol azelate), Poly(trimethylene adipate) (PTA), Poly(tetramethylene glutarate), Poly(dodecanediol sebacate), and Poly(glycerol sebacate) (branched), or a mixture thereof. In an embodiment of the present invention, the aliphatic polyester diol is derived from a biological material. Examples of bio-based aliphatic polyester diol include: Poly(1,3- propanediol adipate) (bio-PTA), Poly(butanediol succinate) diol (PBS-diol), Polycaprolactone diol (PCL-diol), Poly(glycerol sebacate) (PGS), Poly(1,3-propanediol succinate), Poly(ethylene sebacate), Poly(dodecanediol sebacate), Poly(xylitol adipate), Poly(mannitol sebacate), and Poly(isosorbide succinate), or a mixture thereof. In an embodiment, component (A) has a viscosity ranging from 350 to 5000 cps. As a lower viscosity limit, at least 350 cps, at least 500 cps, at least 750 cps, at least 1000 cps, at least 1500 cps, at least 2000 cps, at least 2500 cps, and at least 3000 cps are mentioned. As an upper viscosity limit, at most 5000 cps, at most 4500 cps, at most 4000 cps, at most 3500 cps, at most 3000 cps, at most 2500 cps, at most 2000 cps, at most 1500 cps, and at most 1000 cps are mentioned. Ranges and sub-ranges based on a selection of a lower limit and an upper Attorney Docket 40787 / 41 BIOB-002 / 01WO limit from the foregoing are mentioned. Exemplary viscosity ranges include low-viscosity formulations having a viscosity of 350 to 3000 cps, 500 to 2500 cps, and 1000 to 2000 cps and also include high-viscosity formulations having a viscosity of 1500 to 5000 cps, 2000 to 4500 cps, and 2500 to 3500 cps. Further, component (A) can be diluted with water on site at the time of preparation of the adhesive composition. Component (B) Component (B) contains an aliphatic isocyanate and / or a cycloaliphatic isocyanate. In an embodiment, component (B) has low VOC content or is free from (i.e., has zero) VOCs. As low VOC content, it is envisioned that there is less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.05 wt%, less than 0.01 wt% total VOCs. In an embodiment, component (B) is water-based (i.e., is contained in water as a solvent). In an embodiment, component (B) is free from organic solvents. The aliphatic isocyanate and / or cycloaliphatic isocyanate may be any compound comprising one or more isocyantate moiety (NCO) which is not directly attached to an aromatic ring. In an embodiment, the aliphatic and / or cycloaliphatic isocyanate include 1,6- hexamethylene diisocyanate (HDI; formula (IX)), HDI isocyanurate trimer (formula (X)), 1- isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI; formula (XI)), and 4,4′-diisocyanato dicyclohexylmethane (H12MDI or hydrogenated MDI; formula (XII)), tetramethylxylylene diisocyanate (TMXDI; formula (XIII)), pentamethylene diisocyanate (PDI; formula (XIV)), or mixtures thereof. Attorney Docket 40787 / 41 BIOB-002 / 01WO (IX)

[0003] Attorney Docket 40787 / 41 BIOB-002 / 01WO In an embodiment, component (B) has a viscosity ranging from 400 to 650 cps, a viscosity ranging from 425 to 600 cps, a viscosity ranging from 450 to 550 cps, or a viscosity ranging from 475 to 525 cps. Additives The component (A) and / or component (B) may include an optional additive component. Exemplary additive components include one or more of a defoamer, a thickener, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and / or a crosslinker. As an example, component (A) may further comprise an additive. In an embodiment, component (A) further comprises a catalyst and / or a crosslinker. Attorney Docket 40787 / 41 BIOB-002 / 01WO Where the additive is a nanotube or a microcarrier, the nanotube and / or microcarrier may contain additives including at least one of titanium dioxide, a pigment, and an antimicrobial agent. Exemplary catalysts include catalysts include tertiary amines, Mannich bases formed from secondary amines, nitrogen-containing bases, alkali metal hydroxides, alkali phenolates, alkali metal alcoholates, hexahydrothiazines, and organometallic compounds. An exemplary catalyst is dibutyltin dilaurate, an organotin compound. The catalyst may be added, in amount from 0.001 wt % to 10 wt %, based on the total weight of the system. The catalyst may accelerate the curing time of isocyanate moieties (e.g., in the isocyanate component or in prepolymers) and active hydrogens (e.g., polyols and / or chain extenders) to offer mechanical properties. An exemplary antimicrobial agent is a 2:1 blend of emulsified water-based silver solution and zinc-pyrithione. Dyes and / or pigments (such as titanium dioxide and / or carbon black), may be included in the additive component to impart color properties to the adhesive composition. Pigments may be in the form of solids or a dispersion in a resin carrier. Reinforcements (e.g., flake or milled glass and / or fumed silica), may be used to impart certain properties. The adhesive composition may be a curable composition that includes curing agent / hardener component in addition to the adhesive composition or as part of the adhesive composition. The amount of the hardener component used may vary depending on whether the hardener component is used in addition to or as part of the adhesive composition. In exemplary embodiments, an amine-based hardener (e.g., one that is known in the art for use in curing epoxy systems) may be excluded because the sprayable polyurethane systems rely on urethane curing chemistry due to minimal residual epoxy content. Attorney Docket 40787 / 41 BIOB-002 / 01WO Other additives include, e.g., UV light stabilizers, antioxidants, air release agents, and adhesion promoters, which may be independently used depending on the desired characteristics of the adhesive composition. The additives addition amount will vary depending upon the end use. In an embodiment, the total amount of all additives (based on the total of the adhesive composition including components (A) and (B)) is no more than 25 wt% no more than 20 wt%, no more than 15 wt%, not more than 10 wt%, or no more than 5 wt%. As an example, where the additive is a defoamer, the total amount is 2 to 9 wt%, 3 to 8 wt%, or 4 to 7 wt%. Alternatively, where the coting composition contains a UV light stabilizer, the amount ranges from 1 to 4 wt% or 2 to 3 wt%. Other exemplary additives and amounts include: A reactive surfactant, for example 3-n-pentadecylphenol, with an equivalent weight of from 250 to 300, at an amount of from 1 to 5 wt% or 2 to 4 wt%. A diamine with an equivalent weight ranging from 130 to 160, and an amount of from 3 to 9 wt% or 5 to 7 wt%. An antimicrobial agent, for example, silver solution and zinc pyrithione, at an amount of from 0.5 to 1.5 wt% or 0.75% to 1.25%. Kits The present invention includes an embodiment where a kit is provided such that component (A) and component (B) are contained in discrete and separate containers together with instructions for preparing and / or using the adhesive composition. In the kits of the present invention, the additives may be present in component (A) and / or component (B). Alternatively, the additives may be contained in their own separate container(s) for addition as applicable to the desired use. For example, dyes and / or pigments Attorney Docket 40787 / 41 BIOB-002 / 01WO may be stored in a separate container in the kit. As an example, component (A) may further comprise an additive. In an embodiment, component (A) further comprises a catalyst and / or a crosslinker. Storage temperatures for the kit (and independently for components (A) and / or component (B)) should be 45° to 90°F, 55° to 85°F, or 60° to 80°F. Freezing temperatures, direct sunlight, & moisture should be avoided. Further, the kit (and independently for components (A) and / or component (B)) should not be exposed to direct heat and / or should be kept away from heat sources. In an embodiment, the container containing component (A) and the container containing component (B) are in separate chambers of a delivery device, wherein each container is connected to a mixing chamber by way of a tube, a channel, or other delivery vehicle. In this embodiment, the delivery device further comprises a tip, tube, channel or other outlet from the mixing chamber for application of the adhesive to the desired surface. Method of Making an Adhesive Composition In an embodiment, the adhesive composition is prepared by: (1) Stirring, shaking, or agitating component (A) comprising a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol for a time and under conditions to fully disperse the hydroxyl-containing compound and organic acid amine complex; (2) Stirring, shaking, or agitating a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate for a time and under conditions to fully disperse the aliphatic isocyanate and / or a cycloaliphatic isocyanate; and (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form an adhesive composition. Attorney Docket 40787 / 41 BIOB-002 / 01WO In an embodiment, the stirring, shaking, or agitating of component (A) and of component (B) may be at the same time (i.e., simultaneously) or at different times. In either case, the mode, time, and / or condition of dispersing the component may be different or the same. The time and conditions for stirring, shaking, or agitating in (1) and / or (2) is not particularly limited so long as it is sufficient to ensure that component (A) and component (B), respectively, are fully dispersed in the solvent. The time and conditions would be understood to the skilled artisan. Exemplary, times are from 15 seconds to 5 minutes, from 30 seconds to 4 minutes, from 1 minute to 3 minutes. Stirring can be accomplished by using a jiffy blade mixer at a slow speed (e.g., 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm). Alternatively, where component (A) and component (B) are contained in a two-chamber delivery device, hand shaking or agitation may be preferred. Mixing in (3) is for a time sufficient to substantially blend components (A) and (B). “Substantially blend” in this context means that components (A) and (B) are mixed well and in a manner that permits creation of an approximately uniform dispersion. In an embodiment, the mixing time is from 30 seconds to 5 minutes, from 1 minute to 4 minutes, from 2 minutes to 3 minutes. In an embodiment, the mixing ratio of components (A) and (B) is 0.8:1.2 to 1.2 to 0.8, 0.9:1.1 to 1.1:0.9, 0.95:1.05 to 1.05:0.96, or 1:1. Thus, in an embodiment, components (A) and (B) are present in the two-component adhesive system and / or the adhesive composition at a ratio of 0.8:1.2 to 1.2 to 0.8, 0.9:1.1 to 1.1:0.9, 0.95:1.05 to 1.05:0.96, or 1:1. In the preparation method above, the adhesive composition may optionally be allowed stand for a time ranging from 30 seconds to 5 minutes, from 1 minute to 4 minutes, from 2 minutes to 3 minutes prior to being applied to a surface of a material. This standing time initiates the reaction between the hydroxyl-containing compound in component (A) and the Attorney Docket 40787 / 41 BIOB-002 / 01WO aliphatic isocyanate and / or a cycloaliphatic isocyanate in component (B), which may help with curing of the adhesive composition and increase the durability of the bond formed between the two surfaces to be adhered. The adhesive composition of the present invention prepared by the foregoing method has a pot life of from 1 to 5 hours, from 1.5 to 4 hours, or from 2 to 3 hours at 75°F and 50% RH. In an embodiment, the adhesive composition has low VOC content or is free from (i.e., has zero) VOCs. As low VOC content, it is envisioned that there is less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.05 wt%, less than 0.01 wt% total VOCs. In an embodiment, the adhesive composition has no odor after mixing. In an embodiment, the adhesive composition has a pH after mixing ranging from 6.5 to 7.5, from 6.7 to 7.3, from 6.9 to 7.1. In an embodiment, the adhesive composition has a viscosity after mixing ranging from 350 to 5000 cps. As a lower viscosity limit, at least 350 cps, at least 500 cps, at least 750 cps, at least 1000 cps, at least 1500 cps, at least 2000 cps, at least 2500 cps, and at least 3000 cps are mentioned. As an upper viscosity limit, at most 5000 cps, at most 4500 cps, at most 4000 cps, at most 3500 cps, at most 3000 cps, at most 2500 cps, at most 2000 cps, at most 1500 cps, and at most 1000 cps are mentioned. Ranges and sub-ranges based on a selection of a lower limit and an upper limit from the foregoing are mentioned. Exemplary viscosity ranges include low-viscosity formulations having a viscosity of 350 to 3000 cps, 500 to 2500 cps, and 1000 to 2000 cps and also include high-viscosity formulations having a viscosity of 1500 to 5000 cps, 2000 to 4500 cps, and 2500 to 3500 cps. The adhesive composition contains a total of at least 24%, at least 25 wt%, at least 27.5 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, or at least 60 wt% of bio-based materials (e.g., a plant-based and / or bio- Attorney Docket 40787 / 41 BIOB-002 / 01WO renewable polymer). The adhesive composition contains a total of at most 95wt%, at most 90 wt%, at most 85 wt%, at most 80 wt%, at most 75 wt%, at most 70 wt%, at most 65 wt%, at most 60 wt%, at most 55 wt%, at most 50 wt%, at most 45 wt%, at most 40 wt%, or at most 35 wt% of bio-based materials (e.g., a plant-based and / or bio-renewable materials). In an embodiment of the invention is any range or sub-range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. In an embodiment, after mixing, the adhesive composition containing component (A) and component (B) has a high solids content of over 60%, over 70%, over 75%, over 80%, over 85%, or over 90%, for example from 60 to 95%, from 70 to 95%, from 75 to 90% or from 80 to 90%. This very high solids content reduces transportation costs. Depending upon the surface to be treated, the application method, and the desired application thickness, among other factors, the adhesive composition of the present invention may be diluted by up to 50% (i.e., add an equal amount of solvent to the volume of the mixed adhesive composition), up to 40%, up to 30%, up to 25%, up to 20%, up to 15%, or up to 10% with a solvent after components (A) and (B) are mixed. In this regard, there would be a corresponding decrease in the solids content of the adhesive composition to be applied. The solvent is preferably water. The adhesive composition of the present invention may be applied to a surface of a material after mixing components (A) and (B). After components (A) and (B) are mixed together there is less than 10 wt%, less than 7.5 wt%, less than 5 wt%, less than 2.5 wt%, or no free aliphatic isocyanate (and / or cycloaliphatic isocyanate) in the adhesive composition. Not to be bound to any specific theory or mechanism, but any free isocyanate is expected to immediately convert to aliphatic (and / or cycloaliphatic) polyurethane which is also water-based. Attorney Docket 40787 / 41 BIOB-002 / 01WO Method of Using an Adhesive Composition and Resulting Material Construct In an embodiment is a method of adhering a surface of a first material to a surface of second material by: (1) applying a layer of an adhesive composition prepared by the foregoing method to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles) and (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to cure. In an alternative embodiment, is a method of adhering a surface of a first material to a surface of second material, comprising: (1a) applying a layer of a component (A) defined herein above to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles); (1b) applying a layer of a component (B) defined herein above to the same surface as in (1a) and / or to an untreated surface of a material (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles); (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to cure. In the foregoing methods, application thickness will vary based upon the materials to be adhered, the adherence strength desired, the adhesive composition viscosity, the adhesive composition solids content, whether a catalyst is included, and whether the component (A) and component (B) are mixed before application. In general, the application thickness (of the Attorney Docket 40787 / 41 BIOB-002 / 01WO individual components or the mixed adhesive composition) ranges from 0.001 to 0.500 inches (1 – 500 mils), from 0.002 to 0.250 inches (2 – 250 mils), from 0.003 to 0.200 inches (3 – 200 mils), from 0.004 to 0.100 inches (4 to 100 mils), or from 0.005 to 0.050 inches (5 to 50 mils). Of course, thinner applications are also envisioned of from 1 to 50 mils, 2 to 25 mils, 3 to 20 mils, 4 to 15 mils, or 5 to 10 mils. The adhesive composition may be applied to the surface of a material by brushing, rolling, or spraying. Following contacting of the two surfaces of the materials, the adhesive composition of the present invention has a curing / dry-time ranging from 2 to 15 hours, from 3 to 14 hours, from 4 to 13 hours, from 5 to 12 hours, from 6 to 11 hours, or from 7 to 10 hours, but the drying time varies depending upon the temperature, ventilation, and catalyst system being used. For example, the drying time at ambient temperature may be 8 hours or less. The curing in step (3) may be with constant or intermittent pressure to maintain contact between the first and second surfaces for the full curing time or until the two surfaces remain adhered to each other without application of pressure. After preparing the adhesive composition, a process for curing the composition may be used to form a thermoset or cured composition. For example, the composition or formulation may be cured under conventional processing conditions to form an adhesive bond. Curing the adhesive composition may be carried out at curing reaction conditions including a predetermined temperature and for a predetermined period of time sufficient to cure the composition. The curing conditions may be dependent on the various components used in the curable composition such as the hardener used in the formulation. The curing reaction conditions include, e.g., carrying out the reaction under a temperature, generally in the range of from −5° C. to 60° C. (e.g., 0° C. to 50° C., 5° C. to 25° C., etc.). For sprayable applications, the adhesive may be applied to substrates, e.g., using airless sprayers and air- Attorney Docket 40787 / 41 BIOB-002 / 01WO assisted pneumatic sprayers and the like. The applied composition may be cured by heating the composition at the aforementioned curing temperatures. Temperature and humidity directly affect pot life and dry time. Accordingly, in an embodiment the conditions should be between 40 – 95 °F, between 50 and 85 °F, between 60 and 80 °F, or between 65 and 75 °F and the humidity should not exceed 80%, not exceed 70%, not exceed 60%, or not exceed 50%. In an embodiment, the surface to be coated has a moisture content of no more than 25%, no more than 20%, no more than 15%, no more than 10%, or no more than 5% as measured with an electronic moisture meter. Prior to application of the adhesive composition to a surface(s), the surface(s) may pretreated and / or cleaned. In an embodiment, the surface(s) to be adhered may be cleaned prior to application of the adhesive composition. For example, to facilitate proper adherence, the surface can be cleaned to remove dirt, debris, grime, minerals such as lime and calcium, oils, release agents, grease, mud, excess mortar, and mold and mildew, etc. In an embodiment, the surface may be pretreated with a primer (e.g., smooth surfaces) or a sealer or filler to remove pinholes (e.g., porous surfaces). Another envisioned pretreatment includes pointing and / or caulking all cracks. Further, all voids, beeholes, masonry surface defects and openings such as conduits, pipes, drains, door frames, vents, air conditioner openings, electrical openings, control joints, or any dissimilar materials should be repaired using urethane or other approved patching. Another form of surface pretreatment envisioned in the present invention includes fluting, scoring, sandblasting, and / or etching as well as raking joints. In an embodiment, the adhesive composition is not applied where freezing temperatures have existed prior to application. In such a situation, adequate time should be Attorney Docket 40787 / 41 BIOB-002 / 01WO allowed for the application surface to thaw. In an embodiment, air, surface, and material temperatures should be above 40°F (4.4°C) and at least 5°F above the dew point prior to application. Further, it is not desirable to apply the adhesive composition where temperatures are below 40°F or when temperatures are expected to drop below 40°F within 48 hours of application. For exterior surfaces, application should also be avoided if rain, snow, or lower temperatures are expected within 48 hours. Further, the adhesive composition would be adversely affective if relative humidity is greater than 90% and, therefore, it should be avoided. In the case of spills or following application excess adhesive composition can be cleaned up with water. Coated Products The adhesive composition of the present invention finds utility in many different industries including household, oil and gas, steel fabrication, bridge and highway, power generation, pharmaceutical, marine, food processing, veterinary, hospitals, and restaurants. The adhesive composition is suitable for and has excellent adherence properties with a broad scope of materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles. Further, the adhesive composition is suitable for and has excellent adherence properties when two different materials are used. Thus, within the scope of the present invention is a material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises the reaction product of a component (A) comprising a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol and a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, Attorney Docket 40787 / 41 BIOB-002 / 01WO wherein the adhesive contains low or no VOCs and has at least 24 wt% of a bio-based material (e.g., a plant-based and / or bio-renewable polymer). Benefits of Adhesive Composition - Contains at least 28 wt% of a bio-based material (e.g., a plant-based or bio-renewable polymer). - Exhibits excellent adhesion on and between most surfaces. - Chemical and acid resistance is excellent. ^ Examples include: ammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium chloride, trisodium phosphate, ethyl alcohol, isopropyl alcohol, Hyjet #3, Skydrol 500 A & B, hydrochloric acid 10%, phosphoric acid 35%, toluene, xylene, jet fuel - butyl cellosolve, acetone - cellosolve acetate, methyl ethyl ketone, sulfuric acid 20%, acetic acid 24%, trichlorethylene, methyl alcohol, perchlorethylene, beer, cola, milk, mustard, and bleach - Has excellent resistance to mold, mildew, and fungus. - Has good corrosion resistance. - Anti-carbonation protection. - Can be applied directly to metal and concrete. The present invention is exemplified by the following embodiments: [1] A two-component adhesive system comprising: component (A) comprises a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate Attorney Docket 40787 / 41 BIOB-002 / 01WO wherein the adhesive system is water-based and free from volatile organic compounds. [2] The adhesive system of [1], wherein component (A) comprises cardanol. [3] The adhesive system of [2], wherein component (A) comprises from 35 to 55 wt% of tri-unsaturated cardanol, from 25 to 40 wt% mono-unsaturated cardanol, from 15 to 30 wt% bi-unsaturated cardanol, and 1 to 5% saturated cardanol. [4] The adhesive system of [2] or [3], wherein component (A) further comprises cardol, methylcardol, and / or anacardic acid. [5] The adhesive system of [4], wherein component (A) comprises at least 50 wt% cardanol and at least 35 wt % of cardol with the remainder based on a total of 100 wt % of component (A) being methylcardol and / or anacardic acid. [6] The adhesive system of any of [1] – [5], wherein component (A) has a viscosity ranging from 350 to 5000 cps. [7] The adhesive system of any of [1] – [6], wherein component (B) is selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trimer, 1- isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4′-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate. [8] The adhesive system of any of [1] – [7], wherein component (B) has a viscosity ranging from 400 to 650 cps. [9] The adhesive system of any of [1] – [8], wherein component (A) and / or component (B) further comprises an additive and said additive is one or more selected from the group consisting of a defoamer, a thickener, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and a crosslinker.

[0010] The adhesive system of any of [1] – [9], wherein component (A) comprises a hydroxyl-containing compound and an aliphatic polyester diol. Attorney Docket 40787 / 41 BIOB-002 / 01WO

[0011] The adhesive system of any of [1] –

[0010] , wherein component (A) further comprises a catalyst and / or a crosslinker.

[0012] The adhesive system of any of [1] –

[0011] , wherein the ratio of component (A):component (B) is from 0.8:1.2 to 1.2 to 0.8.

[0013] A kit comprising, separately packaged component (A) and component (B) together with instructions for use thereof, wherein component (A) comprises a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate wherein component (A) and component (B) are water-based and free from volatile organic compounds.

[0014] The kit of

[0013] , further comprising one or more separately packaged additives selected from the group consisting of a defoamer, a thickener, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and a crosslinker.

[0015] The kit of claim

[0014] or

[0015] , wherein the component (A) and the component (B) are in separate chambers of a delivery device, wherein each chamber is connected to a mixing chamber by way of a tube, a channel, or other delivery vehicle and wherein the delivery device further comprises a tip, tube, channel or other outlet from said mixing chamber for application of the adhesive to a desired surface.

[0016] A method of making an adhesive composition, comprising (1) Stirring, shaking, or agitating component (A) comprising a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol for a time and under conditions to fully disperse the hydroxyl-containing compound and organic acid amine complex and / or an aliphatic polyester diol; Attorney Docket 40787 / 41 BIOB-002 / 01WO (2) Stirring, shaking, or agitating a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate for a time and under conditions to fully disperse the aliphatic isocyanate and / or a cycloaliphatic isocyanate; and (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form an adhesive composition.

[0017] The method of

[0016] , wherein the mixing ratio of component (A):component (B) is from 0.8:1.2 to 1.2 to 0.8.

[0018] The method of

[0016] or

[0017] , further comprising holding the adhesive composition for a time ranging from 30 seconds to 5 minutes before further use.

[0019] The method of

[0016] –

[0018] , wherein after mixing the adhesive composition has a solids content of 60 to 95%.

[0020] The method of

[0016] –

[0019] , wherein after mixing the adhesive composition has low or no VOCs.

[0021] The method of

[0016] –

[0020] , wherein after mixing the adhesive composition has a viscosity ranging from 350 to 5000 cps.

[0022] A method of adhering a surface of a first material to a surface of second material by: (1) applying a layer of an adhesive composition prepared by the method of any of

[0016] –

[0021] to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles) and (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to cure.

[0023] The method of

[0022] , wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils. Attorney Docket 40787 / 41 BIOB-002 / 01WO

[0024] The method of

[0022] or

[0023] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, aluminum, metal, galvanized steel, ungalvanized steel, tile, and textiles.

[0025] A method of adhering a surface of a first material to a surface of second material, comprising: (1a) applying a layer of a component (A) comprising a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles); (1b) applying a layer of a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate to the same surface as in (1a) and / or to an untreated surface of a material (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles); (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to cure.

[0026] The method of

[0025] , wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils.

[0027] The method of

[0025] or

[0026] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, aluminum, metal, galvanized steel, ungalvanized steel, tile, and textiles.

[0028] A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises the reaction product of a component (A) comprising a hydroxyl-containing compound and an organic acid amine complex or an Attorney Docket 40787 / 41 BIOB-002 / 01WO aliphatic polyester diol and a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, wherein the adhesive contains low or no VOCs and has at least 24 wt% of a bio-based material.

[0029] The material construct of

[0028] , wherein component (A) comprises cardanol.

[0030] The material construct of

[0029] , wherein component (A) comprises from 35 to 55 wt% of tri-unsaturated cardanol, from 25 to 40 wt% mono-unsaturated cardanol, from 15 to 30 wt% bi-unsaturated cardanol, and 1 to 5% saturated cardanol.

[0031] The material construct of

[0029] or

[0030] , wherein component (A) further comprises cardol, methylcardol, and / or anacardic acid.

[0032] The material construct of

[0031] , wherein component (A) comprises at least 50 wt% cardanol and at least 35 wt % of cardol with the remainder based on a total of 100 wt % of component (A) being methylcardol and / or anacardic acid.

[0033] The material construct of

[0028] –

[0032] , wherein component (B) is selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trimer, 1- isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4′-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.

[0034] The material construct of

[0028] –

[0033] , wherein the adhesive further comprises an additive and said additive is one or more selected from the group consisting of a defoamer, a thickener, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and a crosslinker.

[0035] The material construct of

[0028] –

[0034] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, aluminum, metal, galvanized steel, ungalvanized steel, tile, and textiles. Attorney Docket 40787 / 41 BIOB-002 / 01WO

[0036] The material construct of any of

[0028] –

[0035] , wherein component (A) comprises a hydroxyl-containing compound and an aliphatic polyester diol.

[0037] The material construct of any of

[0028] –

[0036] , wherein component (A) further comprises a catalyst and / or a crosslinker.

[0038] The adhesive system of any of

[0028] –

[0037] , wherein the ratio of component (A):component (B) is from 0.8:1.2 to 1.2 to 0.8. In the context of the present description, all publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth, and shall be considered part of the present disclosure in their entirety. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control. The descriptions of the various embodiments of the present invention have been presented for purposes of illustration, but are not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others or ordinary skill in the art to understand the embodiments disclosed herein. Except where expressly noted, trademarks are shown in upper case. Unless stated otherwise, all percentages, parts, ratios, etc., are by weight. Attorney Docket 40787 / 41 BIOB-002 / 01WO When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values recited when defining a range. Further, where a numerical limit or range is stated herein, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out. Further, unless otherwise explicitly stated to the contrary, when one or multiple ranges or lists of items are provided, this is to be understood as explicitly disclosing any single stated value or item in such range or list, and any combination thereof with any other individual value or item in the same or any other list. When the term “about” is used, it is used to mean a certain effect or result can be obtained within a certain tolerance, and the skilled person knows how to obtain the tolerance. When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim, closing the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears Attorney Docket 40787 / 41 BIOB-002 / 01WO in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The transitional phrase "consisting essentially of" limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention. A “consisting essentially of” claim occupies a middle ground between closed claims that are written in a “consisting of” format and fully open claims that are drafted in a “comprising” format. Optional additives as defined herein, at a level that is appropriate for such additives, and minor impurities are not excluded from a composition by the term “consisting essentially of”. As used herein, an "embodiment" means that a particular feature, structure or characteristic is included in at least one or more manifestations, examples, or implementations of this invention. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art. Combinations of features of different embodiments are all meant to be within the scope of the invention, without the need for explicitly describing every possible permutation by example. Thus, any of the claimed embodiments can be used in any combination. Further, unless expressly stated to the contrary, “and / or” refers to an inclusive and not to an exclusive. Thus, “and / or” should be understood to mean “either or both” of the elements so conjoined, e.g., elements that are conjunctively present in some cases and disjunctively present in other cases. For example, a condition A and / or B, is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Attorney Docket 40787 / 41 BIOB-002 / 01WO The use of "a" or "an" to describe the various elements and components herein is merely for convenience and to give a general sense of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. Similarly, the adjective “another,” when used to introduce an element, is intended to mean one or more elements. The terms “including” and “having” are intended to be inclusive such that there may be additional elements other than the listed elements. The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description. As used herein, the phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials. The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description. Although this invention has been described with a certain degree of particularity, it is to be understood that the present disclosure has been made only by way of illustration and that numerous changes in the details of construction and arrangement of parts may be resorted to without departing from the spirit and the scope of the invention. The above description is presented to enable a person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other Attorney Docket 40787 / 41 BIOB-002 / 01WO embodiments and applications without departing from the spirit and scope of the invention. Thus, this invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. It is, therefore, to be understood that within the scope of the accompanying claims, the invention may be practiced otherwise than as specifically described herein. Having generally described this invention, a further understanding can be obtained by reference to certain specific examples, which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified. EXAMPLE An adhesive composition of the present invention was prepared and used to adhere two pieces of wood (poplar) as shown in Fig.1. Wood adhered with the adhesive composition of the present invention was compared with Liquid Nails (manufactured by PPG). The adhesive composition of the present invention significantly outperformed Liquid Nails with respect to adherence capacity. Lap shear testing (wood:wood and metal:metal) and shore hardness testing was also conducted on the adhesive composition of the present invention: Inventive Example Bio-Based Content30%Lap Shear – Wood: Wood (Mpa) Lap Shear – Metal:Metall (Mpa) Shore Hardness37.1 (D) Attorney Docket 40787 / 41 BIOB-002 / 01WO Numerous modifications and variations on the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the accompanying claims, the invention may be practiced otherwise than as specifically described herein.

Claims

Attorney Docket 40787 / 41 BIOB-002 / 01WO CLAIMS What we claim is 1. A two-component adhesive system comprising: component (A) comprises a hydroxyl-containing compound and an organic acid amine complex or an aliphatic polyester diol and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate wherein the adhesive system is water-based and has low or is free from volatile organic compounds.

2. The adhesive system of claim 1, wherein component (A) comprises cardanol.

3. The adhesive system of claim 2, wherein component (A) comprises from 35 to 55 wt% of tri-unsaturated cardanol, from 25 to 40 wt% mono-unsaturated cardanol, from 15 to 30 wt% bi-unsaturated cardanol, and 1 to 5% saturated cardanol.

4. The adhesive system of claim 2, wherein component (A) comprises at least 50 wt% cardanol and at least 35 wt % of cardol with the remainder based on a total of 100 wt % of component (A) being methylcardol and / or anacardic acid.

5. The adhesive system of claim 1, wherein component (B) is selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trimer, 1-isocyanato- 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4′-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.Attorney Docket 40787 / 41 BIOB-002 / 01WO 6. The adhesive system of claim 1, wherein the ratio of component (A):component (B) is from 0.8:1.2 to 1.2 to 0.

8.

7. The adhesive system of claim 1, wherein component (A) and / or component (B) further comprises an additive and said additive is one or more selected from the group consisting of a defoamer, a thickener, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and a crosslinker.

8. A kit comprising, separately packaged component (A) and component (B) together with instructions for use thereof, wherein component (A) comprises a hydroxyl-containing compound and an organic acid amine complex or an aliphatic polyester diol and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate wherein component (A) and component (B) are water-based and free from volatile organic compounds, and optionally one or more additives selected from the group consisting of a defoamer, a thickener, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and a crosslinker, which may be separately packaged or packaged as a part of component (A) and / or component (B).

9. The kit of claim 8, wherein the component (A) and the component (B) are in separate chambers of a delivery device, wherein each chamber is connected to a mixing chamber by way of a tube, a channel, or other delivery vehicle and wherein the deliveryAttorney Docket 40787 / 41 BIOB-002 / 01WO device further comprises a tip, tube, channel or other outlet from said mixing chamber for application of the adhesive to a desired surface.

10. A method of making an adhesive composition, comprising (1) Stirring, shaking, or agitating component (A) comprising a hydroxyl-containing compound and an organic acid amine complex or an aliphatic polyester diol for a time and under conditions to fully disperse the hydroxyl-containing compound and organic acid amine complex or an aliphatic polyester diol; (2) Stirring, shaking, or agitating a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate for a time and under conditions to fully disperse the aliphatic isocyanate and / or a cycloaliphatic isocyanate; and (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form an adhesive composition.

11. The method of claim 10, wherein after mixing the adhesive composition has a solids content of 60 to 95% and has low or no VOCs.

12. A method of adhering a surface of a first material to a surface of second material by: (1) applying a layer of an adhesive composition prepared by the method of claim 10 to a surface of one or both materials, wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, and textile, and (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to cure.Attorney Docket 40787 / 41 BIOB-002 / 01WO 13. The method of claim 12, wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils.

14. The method of claim 12, wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, aluminum, metal, galvanized steel, ungalvanized steel, tile, and textiles.

15. A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises the reaction product of a component (A) comprising a hydroxyl-containing compound and an organic acid amine complex and / or an aliphatic polyester diol and a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, wherein the adhesive contains low or no VOCs and has at least 24 wt% of a bio-based material.

16. The material construct of claim 15, wherein component (A) comprises cardanol.

17. The material construct of claim 16, wherein component (A) comprises from 35 to 55 wt% of tri-unsaturated cardanol, from 25 to 40 wt% mono-unsaturated cardanol, from 15 to 30 wt% bi-unsaturated cardanol, and 1 to 5% saturated cardanol.

18. The material construct of claim 16, wherein component (A) comprises at least 50 wt% cardanol and at least 35 wt % of cardol with the remainder based on a total of 100 wt % of component (A) being methylcardol and / or anacardic acid.Attorney Docket 40787 / 41 BIOB-002 / 01WO 19. The material construct of claim 15, wherein component (B) is selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trimer, 1- isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4′-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.

20. The material construct of claim 15, wherein the adhesive further comprises an additive and said additive is one or more selected from the group consisting of a defoamer, a thickener, an emulsifier, dyes, a pigment, an antimicrobial agent, a nanotube, a microcarrier, a curative agent, a catalyst, a surfactant, a plasticizer, a filler, reinforcements, a solvent, a chain extender, and a crosslinker.

21. The material construct of claim 15, wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, aluminum, metal, galvanized steel, ungalvanized steel, tile, and textiles.

Images