Functionalized plant oil-based quaternary amines for enhanced miscibility in biobased formulations

Abstract

A modified plant oil-based quaternary amine with enhanced miscibility in biobased formulations, as well as methods of making the modified plant oil-based quaternary amine, methods of using the modified plant oil-based quaternary amine, and products incorporating and / or derived from the modified plant oil-based quaternary amine. The modified plant oil-based quaternary amine has sufficient miscibility to be useful in coatings and adhesives acting on many materials including ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic. Further, as the modified plant oil-based quaternary amine is a biologically derived material, the coatings and adhesives may be composed of bio-based material(s) totaling from 24% to 95%.

Description

[0001] TITLE OF THE INVENTION

[0002] FUNCTIONALIZED PLANT OIL-BASED QUATERNARY AMINES FOR ENHANCED MISCIBILITY IN BIOBASED FORMULATIONS

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] The present application claims priority to U.S. Provisional Appl. No. 53 / 666,944, filed July 2, 2024, the entire contents of which are incorporated herein by reference.

[0005] FIELD OF THE INVENTION

[0006] The present invention provides a modified plant oil-based quaternary amine (interchangeably referred to herein as a “functionalized plant oil”) with enhanced miscibility in biobased formulations. The present invention also provides methods of making the modified plant oil-based quaternary amine, methods of using the modified plant oil-based quaternary amine, and products incorporating and / or derived from the modified plant oilbased quaternary amine. The modified plant oil-based quaternary amine has sufficient miscibility to be useful in coatings and adhesives acting on many materials including ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic. Further, as the modified plant oil-based quaternary amine is a biologically derived material, the coatings and adhesives may be composed of bio-based material(s) totaling from 24% to 95%.

[0007] DISCUSSION OF THE BACKGROUND

[0008] 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, most bio-based oils are not miscible in water and therefore these alternatives typically contain volatile organic compounds and / or strong off-gassing odors.

[0009] One alternative that has been pursued is adhesives based on soybean oil. Soybean oil is a renewable resource with potential for various applications in the materials industry. However, its limited miscibility in many biobased solvents and resins hinders its widespread use in formulations for coatings and adhesives.

[0010] In view of the foregoing, there remains a critical need in the art to develop safe and effective adhesives.

[0011] SUMMARY OF THE INVENTION

[0012] It is an object of the present invention to provide modified plant (e.g., vegetable and tree-based) oil with enhanced compatibility with other biobased components, which is crucial for developing sustainable and high-performance materials.

[0013] It is an object of the present invention to provide a functionalized plant oil which has quaternary amines and multiple hydroxyl groups produced from a reaction of an epoxidized plant oil with a tertiary amine.

[0014] It is an object of the present invention to provide a biobased formulation containing the functionalized plant oil.

[0015] It is an object of the present invention to provide a method of making a functionalized plant oil by reacting an epoxidized plant oil with a tertiary amine. It is an object of the present invention to provide a coating or adhesive composition comprising the functionalized plant oil.

[0016] It is an object of the present invention to provide a two-component coating system containing: component (A) comprising the functionalized plant oil comprising quaternary amines and multiple hydroxyl groups produced from the reaction of an epoxidized plant oil with a tertiary amine, and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate wherein the coating system is water-based and free from volatile organic compounds.

[0017] It is an object of the present invention to provide a method of making a coating composition, by

[0018] (1) Stirring, shaking, or agitating a component (A) comprising a hydroxyl-containing compound for a time and under conditions to fully disperse the functionalized plant oil;

[0019] (2) Adding a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, which has been optionally stirred, shaken, or agitated for a time and under conditions to fully disperse the aliphatic isocyanate and / or cycloaliphatic isocyanate; and

[0020] (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form a coating composition.

[0021] It is an object of the present invention to provide a method of coating a surface of a material with a coating composition, comprising: applying a coating composition prepared by the foregoing method to the surface of the material and allowing the coating composition to cure.

[0022] It is an object of the present invention to provide a coated material, wherein said material has a coating thereon wherein the coating comprises the reaction product of a component (A) comprising a functionalized plant oil and a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, wherein the coating contains no VOCs and has at least 24 wt% of a hio-based material.

[0023] It is an object of the present invention to provide a two-component adhesive system comprising: component (A) comprises a functionalized plant oil and an organic acid amine complex 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.

[0024] It is an object of the present invention to provide a method of making an adhesive composition, comprising

[0025] (1) Stirring, shaking, or agitating component (A) comprising a functionalized plant oil and an organic acid amine complex for a time and under conditions to fully disperse the functionalized plant oil and organic acid amine complex;

[0026] (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

[0027] (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form an adhesive composition.

[0028] It is an object of the present invention to provide a method of adhering a surface of a first material to a surface of second material by:

[0029] (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, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic, and

[0030] (2) contacting the surface of the first material to the surface of the second surface; and

[0031] (3) allowing the adhesive composition to cure.

[0032] It is an object of the present invention to provide a method of adhering a surface of a first material to a surface of second material, comprising:

[0033] (la) applying a layer of a component (A) comprising a functionalized plant oil and an organic acid amine complex 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, paper packaging, composites, textile, and plastic;

[0034] (lb) applying a layer of a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate to the same surface as in (la) 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, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic;

[0035] (2) contacting the surface of the first material to the surface of the second surface; and

[0036] (3) allowing the adhesive composition to cure.

[0037] It is an object of the present invention to provide 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 functionalized plant oil and an organic acid amine complex 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. 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.

[0038] DETAILED DESCRIPTION OF THE INVENTION

[0039] 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.

[0040] 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.

[0041] 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.

[0042] The present invention provides a novel approach to functionalize plant oils by reacting the epoxy groups in an epoxidized plant oil with a tertiary amine. This reaction opens the epoxy rings, leading to the formation of quaternary amines and the introduction of multiple hydroxyl groups into the soybean oil structure. The resulting modified soybean oil exhibits improved miscibility in various biobased solvents and resins, making it suitable for use in a wide range of coatings and adhesive formulations.

[0043] Functionalized Plant Oil and Method of Making the Same

[0044] In an embodiment, the present invention provides a modified plant oil-based quaternary amine (i.e., a “functionalized plant oil”) with enhanced miscibility, which makes the compound useful in biobased formulations. The functionalized plant oil comprises quaternary amines and multiple hydroxyl groups and is the product of a reaction of an epoxidized plant oil with a tertiary amine.

[0045] In an embodiment, the epoxidized plant oil is prepared by known methods and the source oil for epoxidation may be any plant oil including, e.g., a vegetable or tree oil. In an exemplary embodiment, the plant oil is poxidized using a suitable epoxidation agent, such as peracetic acid or m-chloroperoxybenzoic acid, to introduce epoxy groups into the triglyceride structure.

[0046] Exemplary epoxidized plant oils include epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

[0047] In an embodiment, the epoxidized plant oil is epoxidized soybean oil. An exemplary structure of the epoxidized soybean oil is as follows:

[0048] In an embodiment, the tertiary amine of the present invention may be any amine in which the nitrogen atom is directly bonded to three carbons of any hybridization which cannot be carbonyl group carbons (i.e., R groups), wherein one or more of the substituent R groups contains a hydroxyl group.

[0049] In an embodiment, the tertiary amine of the present invention may be any having the general formula: wherein R1, R2, and R3arc each independently (i.c., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group. It should be noted that in the context of the present invention, the phrase presented in the format “at least one of A, B, and C” means that it includes only A, only B, only C, as well as combinations of two of A, B, and C plus all three being present.

[0050] Within the present invention the hydroxyl count per molecule can be modulated by using a mixture of tertiary amines. Thus, the term “a tertiary amine” as used herein includes one or more tertiary amines such that any recited tertiary amine may be used alone or in combination with another tertiary amine.

[0051] The linear or branched C1-C12 alkyl may be a linear C1-C12 alkyl or a branched C1-C12 alkyl.

[0052] The C1-C12 alkyl may be a group selected from C1-C12 alkyl, a C1-C10 alkyl, a Ci-Cs alkyl, Ci-Ce alkyl, a C1-C4 alkyl, a C1-C3 alkyl, a C1-C2 alkyl, a C2-C12 alkyl, a C2-C10 alkyl, a C2-C8 alkyl, a C2-C6 alkyl, a C2-C4 alkyl, a C2-C3 alkyl, a C3-C12 alkyl, a C3-C10 alkyl, a C3- Cs alkyl, a C3-C6 alkyl, a C3-C4 alkyl, a Ci alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a Ce alkyl, a C7 alkyl, a Cs alkyl, a C9 alkyl, a C10 alkyl, a C11 alkyl, and a C12 alkyl.

[0053] The C1-C12 alkyl may be substituted by a substituted or unsubstituted C3-12 alicyclic, heterocyclic, aromatic group, or heteroaromatic group, wherein the C3-12 alicyclic or aromatic group may be a group selected from a C3-12 alicyclic group, a C3-10 alicyclic group, C3-8 alicyclic group, C3-6 alicyclic group, a C3-12 heterocyclic group, a C3-10 heterocyclic group, C3- 8 heterocyclic group, C3-6 heterocyclic group, a C3-12 aromatic group, a C3-10 aromatic group, C3-8 aromatic group, C3-6 aromatic group, a C3-12 heteroaromatic group, a C3-10 heteroaromatic group, C3-8 heteroaromatic group, C3-6 heteroaromatic group. The heteroatom may be one or more of O, N, or S.

[0054] The C1-C12 alkyl as defined above may be substituted to contain one, two or three hydroxyl groups. Further, where the C1-C12 alkyl contains a substituted C3-12 alicyclic, heterocyclic, aromatic group, or heteroaromatic group, as defined above, the substituent may be one or more hydroxyl groups, for example one, two, or three hydroxyl groups.

[0055] The C1-C12 alkyl may be alternatively or additionally substituted with an alkyl group, an alkoxy group, a halogen, an ether, or an amine.

[0056] In an embodiment, R1, R2, and R3are each independently a linear or branched C1-C4 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

[0057] In an embodiment, R1, R2, and R3are each independently a linear or branched C1-C4 alkyl with the proviso that at least one of R1, R2, and R3independently contains one, two or three hydroxyl groups.

[0058] In an embodiment, R1, R2, and R3are each independently a linear or branched C1-C4 alkyl with the proviso that at least two of R1, R2, and R3independently contains one, two or three hydroxyl groups.

[0059] In an embodiment, R1, R2, and R3are each independently a linear or branched C1-C4 alkyl with the proviso that each of R1, R2, and R3independently contains one, two or three hydroxyl groups.

[0060] Exemplary tertiary amines include trimethanolamine, triethanolamine, tripropanolamine, dimethylethanolamine, diethylethanolamine, N,N- diisopropylaminoethanol, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, isopropyldiethanolamine, phenyldiethanolamine, 4- [(dimethylamino)methyl]phenol, 1 - [ 1 -hydroxy ethyl(2-hydroxyethyl)amino] ethanol, N,N- bis(2-aminoethyl)ethanolamine, 2-[ethyl(methyl)amino]ethanol, and (3- aminopropyl)diethanolamine.

[0061] In an embodiment, the tertiary amine is triethanolamine.

[0062] As stated above, the functionalized plant oil of the present invention is produced by reacting a epoxidized plant oil as described above with a tertiary amine as described above. In this reaction the epoxy rings open, forming covalent bonds with the amine groups, resulting in quaternary amines and the introduction of multiple hydroxyl groups per triglyceride molecule of the plant oil.

[0063] The reaction may be conducted in an organic solvent. Alternatively, the reaction may be conducted in a solvent that has low or is free from volatile organic compounds, for example water.

[0064] The reaction may be conducted at atmospheric pressure.

[0065] The reaction may be conducted at a temperature ranging from 10 to 50°C, from 15 to 45°C, from 20 to 35°C, from 25 to 30°C, or at ambient temperatures.

[0066] Although the hydroxyl count per molecule of the functionalized plant oil is a function of the epoxidized plant oil and the tertiary amine selected, mentioned values range from 4 to 80, 4 to 72, 4 to 60, 4 to 48, 4 to 36, 4 to 24, 4 to 18, 4 to 12, 6 to 80, 6 to 72, 6 to 60, 6 to 48, 6 to 36, 6 to 24, 6 to 18, 6 to 12, 8 to 80, 8 to 72, 8 to 60, 8 to 48, 8 to 36, 8 to 24, 8 to 18, 8 to 12 hydroxyl groups per molecule of functionalized plant oil.

[0067] Within the present invention the hydroxyl count per molecule can be modulated by using a mixture of tertiary amines. Thus, the term “a tertiary amine” as used herein includes one or more tertiary amines such that any recited tertiary amine may be used alone or in combination with another tertiary amine. The functionalized plant oil contains quaternary amines and multiple hydroxyl groups. These functional groups significantly enhance the oil's miscibility in various biobased solvents and resins due to increased polarity and hydrogen bonding capability.

[0068] The presence of the hydroxyl groups also allows the functionalized plant oil to serve as an intermediate for further chemical modification. For example, the functionalized plant oil may be utilized as one part in a two-part coating or adhesive composition wherein the second part contains an aliphatic isocyanate and / or a cycloaliphatic isocyanate.

[0069] Biobased Formulations

[0070] The functionalized soybean oil can be readily incorporated into various biobased formulations for coatings and adhesives. The improved miscibility ensures uniform dispersion and compatibility with other biobased components, leading to enhanced performance and sustainability.

[0071] The functionalized plant oil of the present invention can be applied in a broad range of biobased materials, including:

[0072] Coatings: Paints, varnishes, lacquers, inks, and wood finishes.

[0073] Adhesives: Wood adhesives, pressure-sensitive adhesives, and laminating adhesives.

[0074] Composites: Reinforcement in biobased composites.

[0075] Sealants: Caulks, sealants, and gaskets.

[0076] Other Applications: Plasticizers, lubricants, and additives for various biobased materials.

[0077] An advantage proffered by the functionalized plant oil is that it is biologically sourced and considered a biomaterial. As such, whether used as an active component, a plasticizer, a lubricant, or an additive, the functionalized plant oil allows the production of compositions that contain from 24% to 95% bio-based materials. The following describes two envisioned uses of the functionalized plant oil of the present invention as a coating or as an adhesive.

[0078] Coatings

[0079] The functionalized plant oil of the present invention can be used in a two-part coating system which contains component (A) the functionalized plant oil and component (B) an aliphatic isocyanate and / or a cycloaliphatic isocyanate. The coating composition of the present invention is water-based and free from volatile organic compounds (“VOC”) including formaldehyde.

[0080] In the coating system, component (A) comprises the functionalized plant oil.

[0081] In an embodiment, component (A) is free from (i.e., has zero) VOCs.

[0082] In an embodiment, component (A) is water-based (i.e., is contained in water as a solvent).

[0083] In an embodiment, component (A) is free from organic solvents.

[0084] It is envisioned that the functionalized plant oil can be admixed with other bio-based hydroxyl -containing compounds including 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. Component (A) can be diluted with water on site at the time of preparation of the coating composition.

[0085] Component (B) contains an aliphatic isocyanate and / or a cycloaliphatic isocyanate.

[0086] In an embodiment, component (B) is free from (i.e., has zero) VOCs. In an embodiment, component (B) is water-based (i.e., is contained in water as a solvent).

[0087] In an embodiment, component (B) is free from organic solvents.

[0088] 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.

[0089] 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.

[0090]

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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 polyurethane coatings. Pigments may be in the form of solids or a dispersion in a resin carrier.

[0096] Reinforcements (e.g., flake or milled glass and / or fumed silica), may be used to impart certain properties.

[0097] The coating system may be a curable composition that includes curing agent / hardener component in addition to the coating system or as part of the coating system. 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 coating system. 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.

[0098] 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 polyurethane coating.

[0099] 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 coating 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%.

[0100] Other exemplary additives and amounts include:

[0101] 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%.

[0102] 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%.

[0103] 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 coating composition.

[0104] 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 may be stored in a separate container in the kit such that they can be added in the desired amount to achieve the tint desired.

[0105] 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.

[0106] The coating composition of the present invention may be applied to a surface of a material after mixing components (A) and (B).

[0107] In an embodiment, the coating composition is first prepared for application by:

[0108] (1) Stirring, shaking, or agitating component (A) for a time and under conditions to fully disperse the functionalized plant oil;

[0109] (2) Adding component (B), which has been optionally stirred, shaken, or agitated for a time and under conditions to fully disperse the aliphatic isocyanate and / or cycloaliphatic isocyanate; and (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B).

[0110] 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).

[0111] 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.

[0112] 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.

[0113] In the preparation method above, the coating 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 functionalized plant oil compound in component (A) and the aliphatic isocyanate and / or a cycloaliphatic isocyanate in component (B), which may help with curing of the coating on the surface of the material.

[0114] The coating 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.

[0115] In an embodiment, the coating composition is VOC-free. In an embodiment, the coating composition has no odor after mixing.

[0116] In an embodiment, the coating 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.

[0117] In an embodiment, the coating composition has a viscosity after mixing ranging from 400 to 650 ops, from 425 to 600 cps, from 450 to 550 cps, or from 475 to 525 cps.

[0118] The coating 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 biorenewable polymer). The coating 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.

[0119] In an embodiment, after mixing, the coating 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.

[0120] Depending upon the surface to be treated, the application method, and the desired coating thickness, among other factors, the coating 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 coating 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. Thinning is also desirable for some applications to avoid lap marks and / or to allow for proper self-leveling characteristics. The solvent is preferably water. 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 coating 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.

[0121] Application thickness should be 1 to 6 mils, 2 to 5 mils, or 3 to 4 mils with each application thereof to achieve a total thickness of 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 coatings 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.

[0122] The coating composition may be applied to the surface of a material by brushing, rolling, or spraying. The coating composition of the present invention has a coverage rate of approximately 250 to 400 sq. ft. per gallon; however, the coverage rate is impacted by the material (e.g., substrate) to be treated, the surface pretreatment, and whether or not the coating composition was diluted before application. The following table includes approximate coverage rates for different substrates: Following application to the surface of a material, the coating composition of the present invention has a 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.

[0123] After preparing the coating 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 a film, a coating, or a solid. Curing the coating 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 coating may be applied to substrates, e.g., using airless sprayers and airassisted pneumatic sprayers and the like. The applied composition may be cured by heating the composition at the aforementioned curing temperatures.

[0124] Following drying of a first layer or when the coating is tack free, a second coating layer may be applied by spraying, rolling, or brushing. However, for proper adhesion, it is desired to apply the second coat within 24 hours, within 18 hours, within 12 hours, or within 6 hours of application of the first coat. If the first coat has dried longer than 24-hours, the surface may be abraded or etched to promote adhesion of the second coat.

[0125] 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%.

[0126] 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.

[0127] Prior to application of the coating composition to a surface, the surface may pretreated and / or cleaned.

[0128] In an embodiment, the surface to be coating may be cleaned prior to application of the coating composition. For example, to facilitate proper penetration and sealing of the coating, 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.

[0129] 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.

[0130] Another form of surface pretreatment envisioned in the present invention includes fluting, scoring, sandblasting, and / or etching as well as raking joints. Pretreating a surface in this manner can increase the absorption, but will also lower coverage rates.

[0131] In an embodiment, the coating composition is not applied where freezing temperatures have existed prior to application. In such a situation, adequate time should be 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 coating 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 coating composition would be adversely affective if relative humidity is greater than 90% and, therefore, it should be avoided.

[0132] In the case of spills or following application excess coating composition can be cleaned up with water.

[0133] The coating composition of the present invention finds utility in many different industries including oil and gas, steel fabrication, bridge and highway, power generation, pharmaceutical, marine, food processing, veterinary, hospitals, and restaurants.

[0134] An exemplary use includes floors of food processing, veterinary, hospitals, restaurants and other facilities that need to have a floor coating with high gloss, mold resistance, and mildew resistance. Other uses include warehouses, food and beverage facilities, USDA inspected facilities, commercial vehicles, airports, stadiums, sound walls, stadiums, direct-to- metal, aluminum & metal, galvanized & ungalvanized steel.

[0135] The coating composition is suitable for and has excellent adherence to properties to a broad scope of materials including ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

[0136] Thus, within the scope of the present invention are materials having a coating made from the coating composition of the present invention. In an embodiment, the coating on the materials is at a total thickness of 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 coatings 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. Adhesive Compositions

[0137] Similar to the foregoing coating composition, the functionalized plant oil can be incorporated into a water-based two-component adhesive system.

[0138] In this embodiment, component (A) contains the functionalized plant oil and an organic acid amine complex.

[0139] 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.

[0140] In an embodiment, component (A) is water-based (i.e., is contained in water as a solvent).

[0141] In an embodiment, component (A) is free from organic solvents.

[0142] As described above, it is envisioned that the functionalized plant oil can be admixed with other bio-based hydroxyl-containing compounds including 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.

[0143] 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 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).

[0144] Component (A) can be diluted with water on site at the time of preparation of the adhesive composition.

[0145] Component (B) for the adhesive composition is as described above in the context of the coating composition. As also described above, 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.

[0146] The present invention includes an embodiment where a kit is provided for the adhesive composition 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.

[0147] In the kits for use with the adhesive composition, 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 may be stored in a separate container in the kit.

[0148] 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.

[0149] In an embodiment, the adhesive composition is prepared by:

[0150] (1) Stirring, shaking, or agitating component (A) comprising a functionalized plant oil and an organic acid amine complex for a time and under conditions to fully disperse the functionalized plant oil and organic acid amine complex;

[0151] (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

[0152] (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form an adhesive composition.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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 functionalized plant oil in component (A) and the 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.

[0158] 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.

[0159] 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.

[0160] In an embodiment, the adhesive composition has no odor after mixing.

[0161] 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.

[0162] 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 biorenewable 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.

[0163] 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.

[0164] 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.

[0165] The adhesive composition of the present invention may be applied to a surface of a material after mixing components (A) and (B).

[0166] 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.

[0167] In an embodiment is a method of adhering a surface of a first material to a surface of second material by:

[0168] (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, paper packaging, composites, textile, and plastic) and

[0169] (2) contacting the surface of the first material to the surface of the second surface; and

[0170] (3) allowing the adhesive composition to cure.

[0171] In an alternative embodiment, is a method of adhering a surface of a first material to a surface of second material, comprising:

[0172] (la) 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, paper packaging, composites, textile, and plastic);

[0173] (lb) applying a layer of a component (B) defined herein above to the same surface as in (la) 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, paper packaging, composites, textile, and plastic);

[0174] (2) contacting the surface of the first material to the surface of the second surface; and

[0175] (3) allowing the adhesive composition to cure.

[0176] 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 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.

[0177] The adhesive composition may be applied to the surface of a material by brushing, rolling, or spraying.

[0178] 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.

[0179] 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 airassisted pneumatic sprayers and the like. The applied composition may be cured by heating the composition at the aforementioned curing temperatures.

[0180] 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%.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] Another form of surface pretreatment envisioned in the present invention includes fluting, scoring, sandblasting, and / or etching as well as raking joints.

[0185] 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 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.

[0186] In the case of spills or following application excess adhesive composition can be cleaned up with water. 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.

[0187] 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, paper packaging, composites, textile, and plastic. Further, the adhesive composition is suitable for and has excellent adherence properties when two different materials are used.

[0188] 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 functionalized plant oil and an organic acid amine complex 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).

[0189] Benefits of the Functionalized Plant Oil

[0190] The functionalized plant oil of the present invention provides one or more of the following advantages:

[0191] - Enhanced miscibility of soybean, com and tree / plant oils in biobased formulations.

[0192] - Allows for the leveling of the coating onto other surfaces.

[0193] - Versatile use in a wide range of coatings and adhesives.

[0194] - Sustainable and renewable source for materials.

[0195] - Improved performance and properties of biobased products.

[0196] - Easy and scalable preparation process. The present invention is exemplified by the following embodiments:

[0197] [1] A functionalized plant oil comprising quaternary amines and multiple hydroxyl groups produced from the reaction of an epoxidized plant oil with a tertiary amine.

[0198] [2] The functionalized plant oil of [1], wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

[0199] [3] The functionalized plant oil of [1] or [2], wherein said epoxidized plant oil is epoxidized soybean oil.

[0200] [4] The functionalized plant oil of any of [1] - [3], wherein said tertiary amine has a structure of the following formula: wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

[0201] [5] The functionalized plant oil of any of [1] - [4], wherein said tertiary amine is selected from the group consisting of trimethanolamine, triethanolamine, tripropanolamine, dimethylethanolamine, diethylethanolamine, N,N-diisopropylaminoethanol, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, isopropyldiethanolamine, phenyldiethanolamine, 4-[(dimethylamino)methyl]phenol, 1-[1 - hydroxyethyl(2-hydroxyethyl)amino]ethanol, N,N-bis(2-aminoethyl)ethanolamine, 2- [ethyl(methyl)amino] ethanol, and (3-aminopropyl)diethanolamine. [6] The functionalized plant oil of any of [1] - [5], wherein said tertiary amine is triethanolamine.

[0202] [7] The functionalized plant oil of any of [1] - [6], wherein the functionalized plant oil has 4 to 80 hydroxyl groups per molecule of the functionalized plant oil.

[0203] [8] The functionalized plant oil of any of [1] - [7], wherein the functionalized plant oil has 6 to 18 hydroxyl groups per molecule of the functionalized plant oil.

[0204] [9] A biobased formulation comprising the functionalized plant oil of any of [1] - [8].

[0205]

[0010] A method of making a functionalized plant oil comprising reacting an epoxidized plant oil with a tertiary amine.

[0206]

[0011] The method of

[0010] , wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

[0207]

[0012] The method of

[0010] or

[0011] , wherein said epoxidized plant oil is epoxidized soybean oil.

[0208]

[0013] The method of any of

[0010] -

[0012] , wherein said tertiary amine has a structure of the following formula: wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

[0209]

[0014] The method of any of

[0010] -

[0013] , wherein said tertiary amine is selected from the group consisting of trimethanolamine, triethanolamine, tripropanolamine, dimethylethanolamine, diethylethanolamine, N,N-diisopropylaminoethanol, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, isopropyldiethanolamine, phenyldiethanolamine, 4-[(dimethylamino)methyl]phenol, 1-[1- hydroxyethyl(2-hydroxyethyl)amino]ethanol, N,N-bis(2-aminoethyl)ethanolamine, 2- [ethyl(methyl)amino] ethanol, and (3-aminopropyl)diethanolamine.

[0210]

[0015] The method of any of

[0010] -

[0014] , wherein said tertiary amine is triethanolamine.

[0211]

[0016] The method of any of

[0010] -

[0015] , wherein said reacting is in the presence of a solvent.

[0212]

[0017] The method of any of

[0010] -

[0016] , wherein the solvent has low or is free of VOCs.

[0213]

[0018] The method of any of

[0010] -

[0017] , wherein the solvent is water.

[0214]

[0019] A coating or adhesive composition comprising the functionalized plant oil of [1],

[0215]

[0020] A two-component coating system comprising: component (A) comprising the functionalized plant oil comprising quaternary amines and multiple hydroxyl groups produced from the reaction of an epoxidized plant oil with a tertiary amine, and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate wherein the coating system is water-based and free from volatile organic compounds.

[0216]

[0021] The coating system of

[0020] , wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

[0217]

[0022] The coating system of

[0020] or

[0021] , wherein said epoxidized plant oil is epoxidized soybean oil.

[0023] The coating system of any of

[0020] -

[0022] , wherein said tertiary amine has a structure of the following formula: wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

[0218]

[0024] The coating system of any of

[0020] -

[0023] , wherein said tertiary amine is selected from the group consisting of trimethanolamine, triethanolamine, tripropanolamine, dimethylethanolamine, diethylethanolamine, N,N-diisopropylaminoethanol, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, isopropyldiethanolamine, phenyldiethanolamine, 4-[(dimethylamino)methyl]phenol, 1-[1- hydroxyethyl(2-hydroxyethyl)amino]ethanol, N,N-bis(2-aminoethyl)ethanolamine, 2- [ethyl(methyl)amino] ethanol, and (3-aminopropyl)diethanolamine.

[0219]

[0025] The coating system of any of

[0020] -

[0024] , wherein said tertiary amine is triethanolamine.

[0220]

[0026] The coating system of any of

[0020] -

[0025] , wherein the functionalized plant oil has 6 to 18 hydroxyl groups per molecule of the functionalized plant oil.

[0221]

[0027] The coating system of any of

[0020] -

[0026] , wherein component (B) is selected from the group consisting of 1 ,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trimer, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4'-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.

[0222]

[0028] The coating system of any of

[0020] -

[0027] , wherein component (B) has a viscosity ranging from 400 to 650 cps.

[0029] The coating system of any of

[0020] -

[0028] , 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.

[0223]

[0030] A method of making a coating composition, comprising

[0224] (1) Stirring, shaking, or agitating a component (A) comprising a hydroxyl-containing compound for a time and under conditions to fully disperse the functionalized plant oil;

[0225] (2) Adding a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, which has been optionally stirred, shaken, or agitated for a time and under conditions to fully disperse the aliphatic isocyanate and / or cycloaliphatic isocyanate; and

[0226] (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form a coating composition.

[0227]

[0031] The method of

[0030] , wherein the mixing ratio of component (A): component (B) is from 0.8:1.2 to 1.2 to 0.8.

[0228]

[0032] The method of

[0030] or

[0031] , further comprising holding the coating composition for a time ranging from 30 seconds to 5 minutes before further use.

[0229]

[0033] The method of any of

[0030] -

[0032] , wherein after mixing the coating composition has a solids content of 60 to 95%.

[0230]

[0034] A method of coating a surface of a material with a coating composition, comprising: applying a coating composition prepared by the method of any of

[0030] -

[0033] to the surface of the material and allowing the coating composition to cure.

[0231]

[0035] The method of

[0034] , wherein the total coating thickness ranges from 1 to 50 mils.

[0036] The method of

[0034] or

[0035] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

[0232]

[0037] A coated material, wherein said material has a coating thereon wherein the coating comprises the reaction product of a component (A) comprising a functionalized plant oil and a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate, wherein the coating contains no VOCs and has at least 24 wt% of a bio-based material.

[0233]

[0038] The coated material of

[0037] , wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

[0234]

[0039] The coated material of

[0037] or

[0038] , wherein said epoxidized plant oil is epoxidized soybean oil.

[0235]

[0040] The coated material of any of

[0037] -

[0039] , wherein said tertiary amine has a structure of the following formula:

[0236] R1. / R2

[0237] R I3wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

[0238]

[0041] The coated material of any of

[0037] -

[0040] , wherein said tertiary amine is selected from the group consisting of trimethanolamine, triethanolamine, tripropanolamine, dimethylethanolamine, diethylethanolamine, N,N -diisopropylaminoethanol, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, isopropyldiethanolamine, phenyldiethanolamine, 4-[(dimethylamino)methyl]phenol, 1-[1 - hydroxyethyl(2-hydroxyethyl)amino]ethanol, N,N-bis(2-aminoethyl)ethanolamine, 2- [ethyl(methyl)amino] ethanol, and (3-aminopropyl)diethanolamine.

[0239]

[0042] The coated material of any of

[0037] -

[0041] , wherein said tertiary amine is triethanolamine.

[0240]

[0043] The coated material of any of

[0037] -

[0042] , wherein the functionalized plant oil has 6 to 18 hydroxyl groups per molecule of the functionalized plant oil.

[0241]

[0044] The coated material of any of

[0037] -

[0043] , wherein component (B) is selected from the group consisting of 1 ,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trirner, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4'-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.

[0242]

[0045] The coated material of any of

[0037] -

[0044] , 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.

[0243]

[0046] The coated material of any of

[0037] -

[0045] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

[0244]

[0047] A two-component adhesive system comprising: component (A) comprises a functionalized plant oil and an organic acid amine complex 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.

[0245]

[0048] The adhesive system of

[0047] , wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

[0246]

[0049] The adhesive system of

[0047] or

[0048] , wherein said epoxidized plant oil is epoxidized soybean oil.

[0247]

[0050] The adhesive system of any of

[0047] -

[0049] , wherein said tertiary amine has a structure of the following formula: wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

[0248]

[0051] The adhesive system of any of

[0047] -

[0050] , wherein said tertiary amine is selected from the group consisting of trimethanolamine, triethanolamine, tripropanolamine, dimethylethanolamine, diethylethanolamine, N,N -diisopropylaminoethanol, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, isopropyldiethanolamine, phenyldiethanolamine, 4-[(dimethylamino)methyl]phenol, 1-[1- hydroxyethyl(2-hydroxyethyl)amino]ethanol, N,N-bis(2-aminoethyl)ethanolamine, 2- [ethyl(methyl)amino] ethanol, and (3-aminopropyl)diethanolamine.

[0249]

[0052] The adhesive system of any of

[0047] -

[0051] , wherein said tertiary amine is triethanolamine.

[0053] The adhesive system of any of

[0047] -

[0052] , wherein the functionalized plant oil has 6 to 18 hydroxyl groups per molecule of the functionalized plant oil.

[0250]

[0054] The adhesive system of any of

[0047] -

[0053] wherein component (B) is selected from the group consisting of 1 ,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trimer, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4'-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.

[0251]

[0055] The adhesive system of any of

[0047] -

[0054] , wherein component (B) has a viscosity ranging from 400 to 650 cps.

[0252]

[0056] The adhesive system of any of

[0047] -

[0055] , 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.

[0253]

[0057] A method of making an adhesive composition, comprising

[0254] (1) Stirring, shaking, or agitating component (A) comprising a functionalized plant oil and an organic acid amine complex for a time and under conditions to fully disperse the functionalized plant oil and organic acid amine complex;

[0255] (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

[0256] (3) Mixing components (A) and (B) for a time sufficient to substantially blend components (A) and (B) to form an adhesive composition.

[0257]

[0058] The method of

[0057] , wherein the mixing ratio of component (A):component (B) is from 0.8: 1.2 to 1.2 to 0.8.

[0059] The method of

[0057] or

[0058] , further comprising holding the adhesive composition for a time ranging from 30 seconds to 5 minutes before further use.

[0258]

[0060] The method of any of

[0057] -

[0059] , wherein after mixing the adhesive composition has a solids content of 60 to 95%.

[0259]

[0061] The method of any of

[0057] -

[0060] , wherein after mixing the adhesive composition has low or no VOCs.

[0260]

[0062] The method of any of

[0057] -

[0061] , wherein after mixing the adhesive composition has a viscosity ranging from 350 to 5000 cps.

[0261]

[0063] A method of adhering a surface of a first material to a surface of second material by:

[0262] (1) applying a layer of an adhesive composition prepared by the method of any of

[0057]

[0263] -

[0062] 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, paper packaging, composites, textile, and plastic, and

[0264] (2) contacting the surface of the first material to the surface of the second surface; and

[0265] (3) allowing the adhesive composition to cure.

[0266]

[0064] The method of

[0063] , wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils.

[0267]

[0065] The method of

[0063] or

[0064] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

[0268]

[0066] A method of adhering a surface of a first material to a surface of second material, comprising:

[0269] (la) applying a layer of a component (A) comprising a functionalized plant oil and an organic acid amine complex 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, paper packaging, composites, textile, and plastic;

[0270] (lb) applying a layer of a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate to the same surface as in (la) 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, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic

[0271] (2) contacting the surface of the first material to the surface of the second surface; and

[0272] (3) allowing the adhesive composition to cure.

[0273]

[0067] The method of

[0066] , wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils.

[0274]

[0068] The method of

[0066] or

[0067] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

[0275]

[0069] 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 functionalized plant oil and an organic acid amine complex 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.

[0276]

[0070] , The material construct of

[0069] , wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

[0071] The material construct of

[0069] or

[0070] , wherein said epoxidized plant oil is epoxidized soybean oil.

[0277]

[0072] The material construct of any of

[0069] -

[0071] , wherein said tertiary amine has a structure of the following formula: wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

[0278]

[0073] The material construct of any of

[0069] -

[0072] , wherein said tertiary amine is selected from the group consisting of trimethanolamine, triethanolamine, tripropanolamine, dimethylethanolamine, diethylethanolamine, N,N-diisopropylaminoethanol, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, isopropyldiethanolamine, phenyldiethanolamine, 4-[(dimethylamino)methyl]phenol, 1-[1 - hydroxyethyl(2-hydroxyethyl)amino]ethanol, N,N-bis(2-aminoethyl)ethanolamine, 2- [ethyl(methyl)amino] ethanol, and (3-aminopropyl)diethanolamine.

[0279]

[0074] The material construct of any of

[0069] -

[0073] , wherein said tertiary amine is triethanolamine.

[0280]

[0075] The material construct of any of

[0069] -

[0074] , wherein the functionalized plant oil has 6 to 18 hydroxyl groups per molecule of the functionalized plant oil.

[0281]

[0076] The material construct of any of

[0069] -

[0075] , wherein component (B) is selected from the group consisting of 1 ,6-hexamethylene diisocyanate (HDI), HDI isocyanurate trimer, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4'-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.

[0077] The material construct of any of

[0069] -

[0076] , 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.

[0282]

[0078] The material construct of any of

[0069] -

[0077] , wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized & ungalvanized steel, tile, paper packaging, composites, textile, and plastic.

[0283] 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.

[0284] 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.

[0285] 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.

[0286] Except where expressly noted, trademarks are shown in upper case. Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.

[0287] 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.

[0288] 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.

[0289] 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.

[0290] 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.

[0291] 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 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.

[0292] 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’.

[0293] 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.

[0294] 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). 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.

[0295] 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.

[0296] As used herein, the phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials.

[0297] 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.

[0298] 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.

[0299] 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 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.

[0300] 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.

[0301] EXAMPLES

[0302] Example 1 -

[0303] An epoxidized soybean oil (Epoxol CAI 18 from ACS) was reacted with triethanolamine (a tertiary amine). This reaction opens the epoxy rings, leading to the formation of quaternary amines and the introduction of multiple hydroxyl groups into the soybean oil structure. The resulting modified soybean oil exhibits improved miscibility in various biobased solvents and resins.

[0304] 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

CLAIMSWhat we claim is1. A functionalized plant oil comprising quaternary amines and multiple hydroxyl groups produced from the reaction of an epoxidized plant oil with a tertiary amine wherein the functionalized plant oil has 6 to 18 hydroxyl groups per molecule of the functionalized plant oil.

2. The functionalized plant oil of claim 1, wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

3. The functionalized plant oil of claim 1, wherein said tertiary amine has a structure of the following formula:R\ -- / R?R I3wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

4. A two-component coating system comprising: component (A) comprising a functionalized plant oil comprising quaternary amines and multiple hydroxyl groups produced from a reaction of an epoxidized plant oil with atertiary amine, wherein the functionalized plant oil has 6 to 18 hydroxyl groups per molecule of the functionalized plant oil, and component (B) comprises an aliphatic isocyanate and / or a cycloaliphatic isocyanate wherein the coating system is water-based and free from volatile organic compounds.

5. The coating system of claim 4, wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

6. The coating system of claim 4, wherein said tertiary amine has a structure of the following formula:wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

7. The coating system of claim 4, wherein component (B) is selected from the group consisting of 1 ,6-hexamethylene diisocyanate (HD1), HDI isocyanurate trimer, 1-isocyanato- 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4'-diisocyanato dicyclohexylmethane, tetramethylxylylene diisocyanate, and pentamethylene diisocyanate.

8. The coating system of claim 4, 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.

9. A method of coating a surface of a material with a coating composition, comprising: applying the coating composition of claim 4 to the surface of the material and allowing component (A) and component (B) in the coating composition to react and cure, wherein the material is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic and wherein the total coating thickness ranges from 1 to 50 mils.

10. A two-component adhesive system comprising: component (A) comprises the functionalized plant oil of claim 1 and an organic acid amine complex, 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.

11. The adhesive system of claim 10, wherein said epoxidized plant oil is selected from the group consisting of epoxidized vegetable oil, epoxidized canola oil, epoxidized safflower oil, epoxidized high oleic sunflower oil, epoxidized neem oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized palm oil, epoxidized broccoli oil, epoxidized olive oil, epoxidized triolein, epoxidized cottonseed oil, and epoxidized com oil.

12. The adhesive system of claim 10, wherein said tertiary amine has a structure of the following formula:wherein R1, R2, and R3are each independently (i.e., may be the same or different) a linear or branched C1-C12 alkyl with the proviso that at least one of R1, R2, and R3contains at least one hydroxyl group.

13. The adhesive system of claim 10, 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.

14. The adhesive system of claim 10, 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.

15. A method of adhering a surface of a first material to a surface of second material by:(1) applying a layer of an adhesive system of claim 10, wherein component (A) and component (B) are allowed to mix, to a surface of one or both materials, wherein the materials may be the same or different materials selected from the group consisting ofceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic, and(2) contacting the surface of the first material to the surface of the second surface; and(3) allowing the adhesive composition to cure, wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils.

16. A method of adhering a surface of a first material to a surface of second material, comprising:(la) applying a layer of a component (A) comprising the functionalized plant oil of claim 1 and an organic acid amine complex 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 steel, ungalvanized steel, tile, paper packaging, composites, textile, and plastic;(lb) applying a layer of a component (B) comprising an aliphatic isocyanate and / or a cycloaliphatic isocyanate to the same surface as in (la) and / or to an untreated surface of a material;(2) contacting the surface of the first material to the surface of the second surface; and(3) allowing the adhesive composition to cure wherein the total thickness of the adhesive composition after said applying ranges from 1 to 500 mils.

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