Non-isocyanate polyurethane composition and process for its preparation

Abstract

A process for the manufacture of a non-isocyanate polyurethane (NIPU) composition by transesterification of a hydroxyl source (e.g., a phenolic compound) with a carbonyl source (e.g., a carbonate or a carbonate precursor) followed by the reaction with a hardening agent (e.g., a phenylalkamine or phenylalkamide), and products and compositions obtained thereby. Among the products are NIPU-based resins, coatings, adhesives, sealants, and foams.

Description

[0001] Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 TITLE OF THE INVENTION NON-ISOCYANATE POLYURETHANE COMPOSITION AND PROCESS FOR ITS PREPARATION CROSS-REFERENCE TO RELATED APPLICATIONS The present application claims priority to U.S. Provisional Appl. No.63 / 707,828, filed October 16, 2024, the entire contents of which are incorporated herein by reference. FIELD OF THE INVENTION The present invention relates to non-isocyanate polyurethane (NIPU)-based resins, coatings, adhesives, sealants, and foams. In particular, the invention relates to a process for the manufacture of a NIPU composition by transesterification of a hydroxyl source (e.g., a phenolic compound) with a carbonyl source (e.g., a carbonate or a carbonate precursor) followed by the reaction with a hardening agent (e.g., a phenylalkamine or phenylalkamide), and products and compositions obtained thereby. DISCUSSION OF THE BACKGROUND Polyurethane chemistry is well-known, but most conventional methodologies utilize toxic and environmentally unfriendly petrochemicals called isocyanates and polyols. NIPU is generally prepared by a reaction of cyclo-carbonates and amines without the use of toxic isocyanates. As such, NIPU is considered a safer alternative. Further, NIPU offers a wide range of, and often improved, properties including porosity, water absorption, chemical resistance, and thermal resistance. As a result, NIPU is seen as a viable technology for coatings, adhesives, sealants, and foams. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 Although NIPUs have emerged as a promising solution, their production often involves complex multi-step processes and / or the use of expensive or less readily available starting materials. In view of the foregoing, there remains a critical need in the art to develop cost- effective, sustainably sourced polyurethane alternatives, and in particular NIPUs. The present invention solves this need. SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-isocyanate polyurethane (NIPU) composition comprising water, tannic acid or other hydroxyl source, dimethyl carbonate, dibutyltin dilaurate, and phenylalkamine or phenylalkamide. It is an object of the present invention to provide a process for preparing a non- isocyanate polyurethane (NIPU) comprising: a) Dissolving a hydroxyl source in a solvent; b) Adding a carbonyl source and a catalyst to the solution resulting in (a) to facilitate a transesterification reaction between the hydroxyl source and the carbonyl source; c) Heating the mixture from (b) to a temperature between 60-120°C and stirring for a period of 1-24 hours; d) Adding a hardening agent to the mixture resulting from (c) and stirring for an additional period of 1-24 hours at room temperature to produce an NIPU; and e) Optionally, isolating and / or purifying the resulting NIPU. It is an object of the present invention to provide a non-isocyanate polyurethane (NIPU) composition produced by transesterification reaction between the hydroxyl source and the carbonyl source in accordance with the foregoing method. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 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 comprising an NIPU prepared by the foregoing method to the surface of a materials selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, and textiles; and allowing the solvent to evaporate. It is an object of the present invention to provide a coated material, wherein said material has a coating thereon wherein the coating comprises an NIPU prepared by the foregoing method. 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: (1) applying a layer of an adhesive composition comprising an NIPU prepared by the foregoing method to a surface of one or both materials, wherein the materials may be the same or different materials and is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, and textiles, and (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to harden and the solvent to evaporate. 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 an NIPU prepared by the foregoing method, 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. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 DETAILED DESCRIPTION OF THE INVENTION Unless specifically defined, all technical and scientific terms used herein have the same meaning as commonly understood by a skilled artisan in chemistry (e.g., polyurethane chemistry), coatings, and adhesives. All methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, with suitable methods and materials being described herein. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. Further, the materials, methods, and examples are illustrative only and are not intended to be limiting, unless otherwise specified. The preferred embodiments of the present invention will now be described with reference to the drawings. Identical elements in the various figures are identified with the same reference numerals. 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. In an embodiment, the present invention provides a process for preparing a non- isocyanate polyurethane (NIPU) composition. The process of the present invention includes the following steps: a) Dissolving a hydroxyl source in a solvent; b) Adding a carbonyl source and a catalyst to the solution resulting in (a) to facilitate a transesterification reaction between the hydroxyl source and the carbonyl source; Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 c) Heating the mixture from (b) to a temperature between 60-120°C and stirring for a period of 1-24 hours; d) Adding a hardening agent to the mixture resulting from (c) and stirring for an additional period of 1-24 hours at room temperature to produce an NIPU; and e) Optionally, isolating and / or purifying the resulting NIPU. In the method of the present invention, a transesterification reaction between a hydroxyl source and a carbonyl source is carried out. Transesterification is a process of exchanging the organic group of an ester with the organic group of an alcohol. In an example, where the hydroxyl source is a phenolic compound the transesterification reaction leads to a partial conversion of the phenolic hydroxyl groups to carboxyalkylated groups. In an embodiment of the present invention, the hydroxyl source provides hydroxyl groups for the polyurethane polymerization. In an embodiment of the present invention, the hydroxyl source is an aromatic compound having two or more hydroxyl substituents. An example is hydroquinone or a phenolic compound. In an embodiment of the present invention, the hydroxyl source is a phenolic compound. Phenolic compounds possess a common chemical structure comprising an aromatic ring with one or more hydroxyl substituents that can be divided into several classes, and the main groups of phenolic compounds include flavonoids, phenolic acids, tannins, stilbenes, and lignans. Members of any of these classes which contain one or more, preferably two or more, hydroxyl groups may be used as the hydroxyl source in the present invention. In an embodiment of the present invention, the phenolic compound is a natural phenolic compound. Advantageously, phenolic compounds represent the most abundant secondary metabolites in plants. In particular, these polyphenol compounds are naturally Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 found in fruits, vegetables, cereals, roots, and leaves among other plant products and can be recovered from biomass. As such, the present invention provides an advantageous benefit in that the primary starting material for the formation of NIPUs is bio-based and sustainably sourced. In an embodiment of the present invention, the hydroxyl source is a condensed tannin. In one approach, the condensed tannin is produced by condensing tannin carbonate (methyl carbonate grafted tannin) with di or poly-aminopolyamino compounds (e.g., hexamethylenediamide). Tannins are extracted from agroforestry biomaterials, such as wood, bark, leaves, and fruits, by water extraction. Tannins can be categorized as hydrolysable tannin or condensed polyflavonoid tannin. Hydrolysable tannin comprises different types of unit structures, including gallic, digallic, and ellagic acids. Condensed tannins comprise flavonoid oligomers of various degrees of polymerization. These units are associated with their precursors, such as flavanes-3-ol and flavanes-3,4-diol, among other flavonoids. Each flavonoid contains two types of phenolic nuclei, which are usually denoted as A and B-ring. whereas the B-ring includes pyrogallol and catechol, among other rare phenols. The A-rings of different tannins possess Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 different chemical structures. The A-rings of tannins extracted from mimosa / wattle, quebracho, Douglas fir, and spruce include resorcinol as main group, whereas those of pine include phloroglucinol as main group. The main polyphenolic pattern is represented using flavonoid analogs that are based on the resorcinol A-ring and pyrogallol B-ring (structure I). This unit structure accounts for 70% of tannin. Unit structure II constitutes 25% of tannin and comprises a resorcinol A-ring and catechol B-ring. The remaining 5% is a mixture of phloroglucinol-pyrogallol (structure III) and phloroglucinol- catechol (structure IV) flavonoids. The remaining components are non-tannins, which are simple carbohydrates, hydrocolloid gums, and nitrogen compounds, i.e., amino and imino acids.

[0002] Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 by phloroglucinol A-ring and catechol B-ring structures (structure IV having one additional hydroxy group at ring atom 4) and the other is represented by phloroglucinol A-ring and phenol B-ring structures (structure IV with no hydroxyl group in position 4’ but a hydroxyl group in position 4). The flavonoid units are generally linked C-4 to C-6, or C-4 to C-8 to form a variety of short chains. Products obtained by C-4-C-6 bonding of units of structure I above are called prorobinetinidin, those obtained by bonding of units of structure II through C-atoms 4 and 6 are called profisetinidin, those obtained by C-4-C-8 bonding of units of structure III are called prodelphinidin and those obtained by linking groups of structure IV through C-atoms 4 and 8 are called procyanidine. The average number of units varies from monomers to octamers with an average degree of polymerization (DP) between 4 and 5. Wattle-extracted tannin comprises on average 4-5 flavonoid units joined together through 4,6- linkages. Pine tannin is phloroglucinolic in nature and its flavonoid units are joined together through C-4-C-8-interflavonoid linkages. Linear polymeric tannins have only C-4-C-6- or C-4-C-8-linkages. However, 4,6- and 4,8-linkages may simultaneously exist in the presence of resorcinolic and phloroglucinolic A-rings. The majority of the flavonoid part of mimosa tannin extract is composed of robinetinidin and fisetinidin but also includes 10-15% of catechin and delphinidin, each of Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 these monomers forming the repeating units of the tannin, the units being respectively linked by C-4-C-6 or C-4-C-8. Maritime and Radiata Pines tannins both present a majority of procyanidin and prodelphinidin flavonoid structures; whereas Quebracho tannin’s major components are profisetinidin, and Mimosa tannin’s prorobinetinidin. In an embodiment of the present invention the hydroxyl source may include, but are not limited to, tannic acid, gallic acid, pyrogallol, catechol, resorcinol, and a condensed tannin. In an embodiment of the present invention, the hydroxyl source is tannic acid. One of skill in the relevant art would readily appreciate methods and manners to dissolve the hydroxyl source in solvent. Where the hydroxyl source is not sufficient soluble in the selected solvent to be dissolved directly, it is well within the professional knowledge and experience of the skilled artisan to select a suitable solvent to pre-dissolve the hydroxyl source where the suitable solvent is one that does not substantially impede the transesterification reaction and / or lead to the formation of undesirable by-products. In an embodiment of the present invention the carbonyl, the carbonyl source is a carbonate or a carbonate precursor. Carbonates for use in the present invention include dialkyl carbonates having 1 to 6, 1 to 4, or 1 to 2 carbon atoms in the alkyl groups, wherein each of the alkyl groups may be the same or different. A carbonate precursor, as used herein, means any compound which under the reaction conditions is converted into a dialkyl carbonate which dialkyl carbonate then is the active species in the transesterification reaction. A particularly preferred dialkylcarbonate is dimethyl carbonate. The solvent for use in the present invention may be water or a C1to C6alkanol, including but not limited to methanol, ethanol, propanol, isopropyl alcohol, 1-butanol, 2- Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 butanol, isobutanol, tert-butyl alcohol, 1-pentanol, isoamyl alcohol, 2-methyl-1-butanol, neopentyl alcohol, 2-pentanol, 3-methyl-2-butanol, 3-pentanol, tert-amyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2- methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3- methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, and 3,3-dimethyl-1- butanol, or mixtures thereof. In an embodiment, the solvent is water. In an embodiment of the present invention, the solvent may also be or serve as the carbonyl source depending upon the solubility of the hydroxyl source in the carbonyl source and, therefore, it is possible to control the total water in the solution. In this embodiment, the total water present at the time of the transesterification reaction is 25 vol % or less, 20 vol % or less, 15 vol % or less, 10 vol % or less, 5 vol % or less, 2.5 vol % or less, 1 vol % or less, 0.5 vol % or less, or even 0 vol %. It is envisioned within an embodiment of the present invention that the hydroxyl source is dissolved in a dialkyl carbonate, which will serve as the solvent in (a) but will also be the carbonyl source in (b). In this embodiment, dimethyl carbonate and diethyl carbonate are mentioned as exemplary dialkyl carbonates. In an object of this embodiment, the hydroxyl source is dissolved in a dialkyl carbonate in (a) and in (b) addition of a further carbonyl source may be omitted, or a second carbonyl source may be added. In the former case, it is envisioned that the catalyst will be added to a solution of the hydroxyl source and the carbonyl source in (b). In another object of this embodiment, (a) and (b) may be combined such that the hydroxyl source, the carbonyl source, and the catalyst are all combined in a single step. In an embodiment of the present invention, the catalyst for the transesterification reaction is a Lewis acid. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 In an embodiment of the present invention, the catalyst for the transesterification reaction is an organotin compound, a metal oxide, a metal carboxylates, a mercaptides oxide, or a combination thereof. Exemplary organotin compounds include Dibutyltin dilaurate, Tributyltin hydride, Tributyltin chloride, Tributyl(1-ethoxyvinyl)tin, Bis(tributyltin), Dibutyltin(IV) oxide, Tributyl(vinyl)tin, Trimethyltin chloride, Hexamethylditin, 2-(Tributylstannyl)thiophene, Dimethyltin dichloride, Dibutyltin dichloride, 2-(Tributylstannyl)pyridine, Allyltributylstannane, Butyltin trichloride, Diphenyltin dichloride, Dibutyltin dilaurate, Dibutyltin diacetate, Tetramethyltin, Tributylphenylstannane, Tributyltin hydride (stabilized), Bis(tributylstannyl)acetylene, Dibutyltin bis(acetylacetonate), Phenyltin trichloride, Tetravinyltin, 2,5-Bis(tributylstannyl)thiophene, Dibutyltin maleate, Butyltin chloride dihydroxide, Tetraphenyltin, Trimethyl(phenyl)tin, Dioctyltin oxide, Butyltinhydroxide- oxide, Triphenyltin hydroxide, Tributyltin chloride-d27, trans-1,2-Bis(tributylstannyl)ethene, 2-(Tributylstannyl)pyrimidine, Dibutyltin oxide, 2-(Tributylstannyl)furan, Tetra-n-butyltin, Tetraallyltin, Trimethyl(tributylstannyl)silane, SnAP OA Reagent, SnAP M Reagent, N- Methyl-4-(tributylstannyl)imidazole, Diphenyltin(IV) oxide, Dimethyltin oxide, (Dimethylamino)trimethyltin(IV), Tetramethyltin, 2-(Tri-n-butylstannyl)oxazole, Tributyl(1- propynyl)tin, Triethyltin bromide, Tetraoctyltin, Bis(trimethylstannyl)acetylene, SnAP Pip Reagent, Azidotrimethyltin(IV), Tripropyltin chloride, SnAP 2,3-Bicyclo-(3,4-Pyr) M Reagent, 1-Tributylstannyl-3,3,3-trifluoro-1-propyne, Tin(II) pyrophosphate, Tributyl[2,2- difluoro-1-(2-methoxyethoxymethoxy)vinyl]stannane, 2-Chloro-5-(tributylstannyl)thiazole, SnAP 3-Spiro-(4-Pip) M Reagent, SnAP-ex 3-N-Boc P Reagent, SnAP-ex 3-O-MOM P, SnAP 2,3-Bicyclo-(3,4-Pyr) M Reagent, 1-Tributylstannyl-3,3,3-trifluoro-1-propyne, Tin(II) pyrophosphate, Tributyl[2,2-difluoro-1-(2-methoxyethoxymethoxy)vinyl]stannane, 2-Chloro- Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 5-(tributylstannyl)thiazole, SnAP 3-Spiro-(4-Pip) M Reagent, SnAP-ex 3-N-Boc P Reagent, and SnAP-ex 3-O-MOM P. In the present invention, the organotin compound (also known as stannanes) can be a dibutyltin compound. Exemplary dibutyltin compounds include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, and dibutyltin oxide. In an embodiment of the present invention, the organotin compound is dibutyltin dilaurate. Oxides, alkyl tin carboxylates, and mercaptides oxides also act as mild Lewis acids to speed up polyurethane formation and are embraced by the present invention. Although dibutyltin dilaurate is the most versatile metal catalyst in polyurethanes catalysis, in recent years dibutyltin dilaurate has faced increased scrutiny in Europe over toxicity concerns. Accordingly, in recognition of the potential application of the NIPU of the present invention in uses for which toxicity may be a consideration, in an embodiment of the present invention the transesterification catalyst is a metal carboxylate. Metals for metal carboxylates include bismuth, zinc, aluminium, titanium, and zirconium, or combinations thereof. Bismuth and zinc catalysts are strongly selective towards the urethane reaction. Bismuth, in particular, can mimic the performance of organotin catalysts and in some instances offers a shorter pot life than organotins. Zinc on the other hand results in increased pot life with a good thorough cure and is especially useful when curing at elevated temperatures (>60 °C). The hydroxyl source and the carbonyl source are provided in a molar ratio in a range from 4:1 to 1:4, from 3.5:1 to 1:3.5, from 3:1 to 1:3, from 2.5:1 to 1 :2.5, from 2:1 to 1:2, from 1.5:1 to 1:1.5 or 1:1. In another example, the cyclic carbonate functional group and amine functional group are provided in a ratio in a range from 2:1 to 1 :2. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 The amount of catalyst used is preferably in the range of from 0.001 to 2.5 mol%, optionally in the range of 0.01 to 1 mol%, optionally in the range of from 0.02 to 0.5 mol% and optionally in the range of from 0.05 to 0.25 mol%, based on total moles of hydroxyl groups present in the hydroxyl source used as reactant. In an embodiment of the present invention, (a) is at room temperature or at a temperature of 30 to 80°C, 35 to 75 °C, 40 to 70°C, 45 to 65°C, or 50 to 60°C. In an embodiment of the present invention, (b) is at room temperature or at a temperature of 30 to 80°C, 35 to 75 °C, 40 to 70°C, 45 to 65°C, or 50 to 60°C. In the context of the present invention, the term “room temperature” means at a temperature ranging from 18 to 26°C, 19 to 25°C, 20 to 24°C or 20 to 22°C. In an embodiment of the present invention, after (b) the mixture is heated to a temperature of 60 to 120°C, 65 to 115°C, 70 to 110°C, 75 to 105°C, 80 to 100°C. In an embodiment of the present invention, the mixture is heated in (c) at a heating rate of 0.5°C / hr to 10°C / hr, 1°C / hr to 5°C / hr, 1.5°C / hr to 4°C / hr, or 2°C / hr to 3°C / hr. In an embodiment of the present invention, stirring in (c) can be accomplished by mechanical or manual stirring. In an embodiment of the present invention, stirring in (c) is at a stirring speed ranging from 100 to 5,000 rpm, 500 to 1,500 rpm, or 700 to 1,000 rpm. In an embodiment of the present invention, stirring in (c) is at a stirring speed ranging from 100 to 500 rpm, 150 to 400 rpm, or 200 to 300 rpm. In an embodiment of the present invention, stirring in (c) is continued for 1 to 24 hours, 2 to 18 hours, 3 to 12 hours, 4 to 8 hours, or 5 to 6 hours. In the reaction product of the transesterification reaction, a part of the phenolic hydroxyl groups are replaced by alkoxycarboxyl groups. In general, 30 to 60%, 35 to 55%, 40 to 50% of the phenolic hydroxyl groups are modified in this way. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 In the method of the present invention, the hardening agent serves to enhance the mechanical properties of the NIPU. In an embodiment of the present invention, the hardening agent is a biobased hardening agent. In an embodiment of the present invention, the hardening agent is a phenylalkamine (also referred to as phenalkamine) or phenylalkamide (also referred to as phenalkamide). Suitable phenylalkamines may include, but are not limited to, phenalkamine curing agents disclosed in U.S. Pat. No.6,262,148, the entire contents of which is incorporated herein by reference, phenylethanolamine and phenylpropanol amine. Suitable phenylalkamides may include, but are not limited to, phenyl acetamide and phenyl propionamide. Another example of phenalkamine curing agents suitable for use in the present invention are biobased phenalkamine produced using cardanol derived from cashew nut shell liquid and an amine in the Mannich reaction. (e.g., Cardolite products 2009SF, 2002, 3025, and 3070). In an embodiment of the present invention, after (c) but before (d) the solvent can be removed and the reaction product can be dried. Drying can be by any means including, but not limited to, vacuum drying or spray drying. In an embodiment, drying of the reaction product is at a temperature in the range of from 20 to 75°C, 30 to 60°C, 35 to 55°C, or 40 to 50°C and the drying time ranges from 6 hours to 96 hours, from 12 hours to 84 hours, from 24 hours to 72 hours or from 36 hours to 60 hours. In an embodiment of the present invention, where the solvent is removed and the reaction product is dried after (c) it is envision that either (i) the reaction product is added to a solution containing the hardening agent, (ii) the reaction product is dissolved in a solvent and the hardening agent is added thereto, or (iii) both the reaction product and hardening agent are dissolved in a solvent(s) and mixed together. The solvent may be any solvent suitable for Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 use with the hardening agent. Exemplary solvents include, but are not limited to may be water or a C1 to C6 alkanol (as defined herein above). In an embodiment of the present invention, in (d) the mixture contains a solid content of the reaction product in the range from 20 to 75 wt%, 25 to 70 wt%, 30 to 65 wt%, 35 to 60 wt%, 40 to 55 wt%. In an embodiment of the present invention, in (d) the mixture contains in the range of 10 to 50, 15 to 45, 20 to 40, or 25 to 35 parts by weight of the hardening agent per 100 parts by weight of the reaction product. In an embodiment of the present invention, following (c): (c’) the solvent is removed and the reaction product is dried and (c’’) the reaction product recovered from step (c’) is dissolved in water at a temperature of 30 to 80°C, 35 to 75 °C, 40 to 70°C, 45 to 65°C, or 50 to 60°C. In an object of this embodiment, the hardening agent is then added to the solution resulting from (c’’) in step (d). In an embodiment of the present invention, the mixture is cooled between (c) and (d) by any known method that is within the purview of the skilled artisan. In an embodiment of the present invention, the mixture is cooled between (c) and (d) at a cooling rate of 0.5°C / hr to 10°C / hr, 1°C / hr to 5°C / hr, 1.5°C / hr to 4°C / hr, or 2°C / hr to 3°C / hr. In an embodiment of the present invention, the hardening agent is added at a temperature of 30 to 80°C, 35 to 75 °C, 40 to 70°C, 45 to 65°C, or 50 to 60°C. In an embodiment of the present invention, the hardening agent is added at room temperature. In the context of the present invention, the term “room temperature” means at a temperature ranging from 18 to 26°C, 19 to 25°C, 20 to 24°C or 20 to 22°C. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 In an embodiment of the present invention, stirring in (d) can be accomplished by mechanical or manual stirring. In an embodiment of the present invention, stirring in (d) is at a stirring speed ranging from 100 to 5,000 rpm, 500 to 1,500 rpm, or 700 to 1,000 rpm. In an embodiment of the present invention, stirring in (d) is at a stirring speed ranging from 100 to 500 rpm, 150 to 400 rpm, or 200 to 300 rpm. In an embodiment of the present invention, stirring in (d) is continued for 1 to 24 hours, 2 to 18 hours, 3 to 12 hours, 4 to 8 hours, or 5 to 6 hours. In an embodiment of the present invention, in step (d) a base is added to adjust the pH to a pH of at least 9, alternatively to a pH of at least 10, alternatively to a pH of at least 11, for example to be in a pH in the range of from 9 to 10 or from 10 to 12. Exemplary bases include of alkali or alkaline earth metal hydroxides. An example of which is sodium hydroxide. The base may be added before or after cooling the mixture to room temperature. In an embodiment of the present invention, a cyclic alkylene carbonate (e.g., a C1to C4alkylene carbonate such as e.g. propylene carbonate) can be added in step (d) as a curing accelerator. If used, the amount of cyclic alkylene carbonate may range of from 1 to 10, from 2 to 8, or from 3 to 5 parts by weight per 100 parts by weight of the reaction product obtained in step (b). In an embodiment of the present invention, the NIPU produced in (d) is isolated and / or purified. In an embodiment of the present invention, the isolation and / or purification is accomplished by precipitation or solvent evaporation. In an embodiment of the present invention is a process for preparing a non-isocyanate polyurethane (NIPU) composition, which includes the following steps: a) Dissolving a phenolic compound in a water; Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 b) Adding a dimethyl carbonate and a dibutyltin dilaurate to the solution resulting in (a) to facilitate a transesterification reaction between the phenolic compound and dimethyl carbonate; c) Heating the mixture from (b) to a temperature between 60-120°C and stirring for a period of 1-24 hours; d) Adding a phenylalkamine or phenylalkamide hardening agent to the mixture resulting from (c) and stirring for an additional period of 1-24 hours at room temperature to produce an NIPU; and e) Optionally, isolating and / or purifying the resulting NIPU. In an embodiment of the present invention, the present invention provides a non- isocyanate polyurethane (NIPU) composition produced by transesterification reaction between the hydroxyl source and the carbonyl source in accordance with the embodiments described above. In an embodiment of the present invention, the present invention provides a NIPU composition comprising water, tannic acid or other hydroxyl source, dimethyl carbonate, dibutyltin dilaurate, and phenylalkamine or phenylalkamide. In an object of this embodiment, the hydroxyl source is selected from the group consisting of tannic acid, gallic acid, pyrogallol, catechol, and resorcinol. Since the non-isocyanate polyurethane compositions of the present invention are devoid of formaldehyde and of isocyanate, the compositions can be used to produce practically VOC-free coatings, adhesives, sealants, foams, and elastomers, meaning that there are no relevant amounts of VOC (volatile organic compounds) present during manufacture and application / service of the coatings, adhesives, sealants, foams, and elastomers. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 In an embodiment of the present invention, 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, or there is 0% (i.e. devoid of) VOCs in the NIPU composition. In an embodiment of the present invention, the NIPU composition contains a total of at least 24%, at least 25 wt%, at least 27.5 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, or at least 60 wt% of bio-based materials (e.g., a plant-based and / or bio-renewable polymer). The NIPU composition contains a total of at most 95wt%, at most 90 wt%, at most 85 wt%, at most 80 wt%, at most 75 wt%, at most 70 wt%, at most 65 wt%, at most 60 wt%, at most 55 wt%, at most 50 wt%, at most 45 wt%, at most 40 wt%, or at most 35 wt% of bio-based materials (e.g., a plant-based and / or bio-renewable materials). In an embodiment of the invention is any range or sub- range bound by a lower (i.e., “at least”) and an upper (i.e., “at most”) limit from those selected above. In an embodiment of the present invention, is a coating, adhesive, sealant, foam, and elastomer each comprising the NIPU of the present invention. In an embodiment of the present invention, 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, or there is 0% (i.e. devoid of) VOCs in a coating, adhesive, sealant, foam, or elastomer incorporating the NIPU of the present invention. In an embodiment of the present invention, the coating, adhesive, sealant, foam, or elastomer further contains an 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. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 Where the additive is a nanotube or a microcarrier, the nanotube and / or microcarrier may contain additives including at least one of titanium dioxide, a pigment, and an antimicrobial agent. Exemplary catalysts include catalysts include tertiary amines, Mannich bases formed from secondary amines, nitrogen-containing bases, alkali metal hydroxides, alkali phenolates, alkali metal alcoholates, hexahydrothiazines, and organometallic compounds. An exemplary catalyst is dibutyltin dilaurate, an organotin compound. The catalyst may be added, in amount from 0.001 wt % to 10 wt %, based on the total weight of the system. The catalyst may accelerate the curing time of isocyanate moieties (e.g., in the isocyanate component or in prepolymers) and active hydrogens (e.g., polyols and / or chain extenders) to offer mechanical properties. An exemplary antimicrobial agent is a 2:1 blend of emulsified water-based silver solution and zinc-pyrithione. Dyes and / or pigments (such as titanium dioxide and / or carbon black), may be included in the additive component to impart color properties to the adhesive composition. Pigments may be in the form of solids or a dispersion in a resin carrier. Reinforcements (e.g., flake or milled glass and / or fumed silica), may be used to impart certain properties. Other additives include, e.g., UV light stabilizers, antioxidants, air release agents, and adhesion promoters, which may be independently used depending on the desired characteristics of the adhesive composition. The additives addition amount will vary depending upon the end use. In an embodiment, the total amount of all additives (based on the total of the adhesive composition including components (A) and (B)) is no more than 25 wt% no more than 20 wt%, no more than 15 wt%, not more than 10 wt%, or no more than 5 wt%. As an example, where the Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 additive is a defoamer, the total amount is 2 to 9 wt%, 3 to 8 wt%, or 4 to 7 wt%. Alternatively, where the coting composition contains a UV light stabilizer, the amount ranges from 1 to 4 wt% or 2 to 3 wt%. Other exemplary additives and amounts include: A reactive surfactant, for example 3-n-pentadecylphenol, with an equivalent weight of from 250 to 300, at an amount of from 1 to 5 wt% or 2 to 4 wt%. A diamine with an equivalent weight ranging from 130 to 160, and an amount of from 3 to 9 wt% or 5 to 7 wt%. 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%. In an embodiment of the present invention, a resulting NIPU foam material can have a density from 1 to 400 kg / m3, from 10 to 300 kg / m3, 25 to 200 kg / m3, 50 to 100 kg / m3. In an embodiment of the present invention, a resulting NIPU foam material can have a Shore A hardness from 1 to 100, from 5 to 80, from 10 to 60, from 25 to 50. In an embodiment of the present invention, the coating, adhesive, sealant, foam, or elastomer contains a total of at least 24%, at least 25 wt%, at least 27.5 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, or at least 60 wt% of bio-based materials (e.g., a plant-based and / or bio-renewable polymer). The coating, adhesive, sealant, foam, or elastomer 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. Advantages provided by the present invention include: Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 - Environmentally friendly: Avoids the use of toxic isocyanates, can be used to produce VOC products, and is sustainably sourced from natural sources. - Cost-effective: Utilizes readily available and inexpensive starting materials. - Simplified process: Involves fewer steps and milder reaction conditions compared to other NIPU synthesis methods. - Biobased hardening agent: Incorporates renewable resources into the NIPU composition. In an embodiment of the present invention is a method of coating a surface of a material with a coating composition, comprising: applying a coating composition comprising an NIPU prepared by the foregoing method to the surface of many different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles and allowing the solvent to evaporate. A coated material, wherein said material has a coating thereon wherein the coating comprises an NIPU prepared by the foregoing method. 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. 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. 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 Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 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. 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. 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. In an embodiment is a method of adhering a surface of a first material to a surface of second material by: (1) applying a layer of an adhesive composition comprising an NIPU prepared by the foregoing method to a surface of one or both materials (wherein the materials may be the same or different materials including ceramic, glass, concrete, wood, metal (including aluminum), galvanized & ungalvanized steel, tile, and textiles) and (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to harden and the solvent to evaporate. In the foregoing methods, application thickness will vary based upon the materials to be adhered, the adherence strength desired, the adhesive composition viscosity, and the adhesive composition solids content. 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), Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 from 0.004 to 0.100 inches (4 to 100 mils), or from 0.005 to 0.050 inches (5 to 50 mils). Of course, thinner applications are also envisioned of from 1 to 50 mils, 2 to 25 mils, 3 to 20 mils, 4 to 15 mils, or 5 to 10 mils. The adhesive composition may be applied to the surface of a material by brushing, rolling, or spraying. Following contacting of the two surfaces of the materials, the adhesive composition of the present invention has a curing / dry-time ranging from 2 to 15 hours, from 3 to 14 hours, from 4 to 13 hours, from 5 to 12 hours, from 6 to 11 hours, or from 7 to 10 hours, but the drying time varies depending upon the temperature, ventilation, and catalyst system being used. For example, the drying time at ambient temperature may be 8 hours or less. A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises an NIPU prepared by the foregoing method, wherein the adhesive contains low or no VOCs and has at least 24 wt% of a bio-based material. The present invention is exemplified by the following embodiments: [1] A non-isocyanate polyurethane (NIPU) composition comprising water, tannic acid or other hydroxyl source, dimethyl carbonate, dibutyltin dilaurate, and phenylalkamine or phenylalkamide. [2] The NIPU composition of [1], wherein the hydroxyl source is selected from the group consisting of tannic acid, gallic acid, pyrogallol, catechol, and resorcinol. [3] A process for preparing a non-isocyanate polyurethane (NIPU) comprising: a) Dissolving a hydroxyl source in a solvent; b) Adding a carbonyl source and a catalyst to the solution resulting in (a) to facilitate a transesterification reaction between the hydroxyl source and the carbonyl source; Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 c) Heating the mixture from (b) to a temperature between 60-120°C and stirring for a period of 1-24 hours; d) Adding a hardening agent to the mixture resulting from (c) and stirring for an additional period of 1-24 hours at room temperature to produce an NIPU; and e) Optionally, isolating and / or purifying the resulting NIPU. [4] The method of [3], wherein the hydroxyl source is a phenolic compound. [5] The method of any of [3] – [4], wherein the phenolic compound is a tannin compound. [6] The method of any of [3] – [5], wherein the phenolic compound is selected from the group consisting of tannic acid, gallic acid, pyrogallol, catechol, resorcinol, and a condensed tannin. [7] The method of any of [3] – [6], wherein the carbonyl source is a carbonate or a carbonate precursor. [8] The method of any of [3] – [7], wherein the carbonyl source is a dialkyl carbonates having 1 to 6 carbon atoms. [9] The method of any of [3] – [8], wherein the carbonyl source is dimethyl carbonate.

[0010] The method of any of [3] – [9], wherein the solvent in (a) is water or a C1 to C6 alkanol.

[0011] The method of any of [3] –

[0010] , wherein the solvent in (a) is water.

[0012] The method of any of [3] –

[0011] , wherein the catalyst for the transesterification reaction in (b) is a Lewis acid.

[0013] The method of any of [3] –

[0012] , wherein the catalyst for the transesterification reaction in (b) is an organotin compound, a metal oxide, a metal carboxylates, a mercaptides oxide, or a combination thereof.

[0014] The method of any of [3] –

[0013] , wherein the catalyst for the transesterification reaction is dibutyltin dilaurate.

[0015] The method of any of [3] –

[0014] , wherein the hydroxyl source and the carbonyl source are provided in a molar ratio in a range from 4:1 to 1:4.

[0016] The method of any of [3] –

[0015] , wherein the catalyst is present in the range of from 0.001 to 2.5 mol% based on total moles of hydroxyl groups present in the hydroxyl source. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57

[0017] The method of any of [3] –

[0016] , wherein the hardening agent is a biobased hardening agent.

[0018] The method of any of [3] –

[0017] , wherein the hardening agent is a phenylalkamine or a phenylalkamide.

[0019] The method of any of [3] –

[0018] , wherein the hardening agent is a biobased phenalkamine produced from cardanol derived from cashew nut shell liquid and an amine in the Mannich reaction.

[0020] The method of any of [3] –

[0019] , further comprising adding a cyclic alkylene carbonate during (d).

[0021] The method of any of [3] –

[0020] , wherein the NIPU produced in (d) is isolated and / or purified.

[0022] The method of any of [3] –

[0021] , comprising: a) Dissolving a phenolic compound in a water; b) Adding a dimethyl carbonate and a dibutyltin dilaurate to the solution resulting in (a) to facilitate a transesterification reaction between the phenolic compound and dimethyl carbonate; c) Heating the mixture from (b) to a temperature between 60-120°C and stirring for a period of 1-24 hours; d) Adding a phenylalkamine or phenylalkamide hardening agent to the mixture resulting from (c) and stirring for an additional period of 1-24 hours at room temperature to produce an NIPU; and e) Optionally, isolating and / or purifying the resulting NIPU.

[0023] A non-isocyanate polyurethane (NIPU) composition produced by transesterification reaction between the hydroxyl source and the carbonyl source in accordance with the method of any of [3] –

[0022] .

[0024] The composition of

[0023] , wherein the composition is free of volatile organic compounds.

[0025] The composition of any of

[0023] –

[0024] , wherein the composition contains at least Attorney Docket No.: BIOB-009 / 01WO 40787 / 57

[0026] A method of coating a surface of a material with a coating composition, comprising: applying a coating composition comprising an NIPU prepared by the method of any of [3] –

[0022] to the surface of a materials selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, and textiles; and allowing the solvent to evaporate.

[0027] A coated material, wherein said material has a coating thereon wherein the coating comprises an NIPU prepared by the method of any of [3] –

[0022] .

[0028] A method of adhering a surface of a first material to a surface of second material by: (1) applying a layer of an adhesive composition comprising an NIPU prepared by the method of any of [3] –

[0022] to a surface of one or both materials, wherein the materials may be the same or different materials and is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, and textiles, and (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to harden and the solvent to evaporate.

[0029] A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises an NIPU prepared by the method of any of [3] –

[0022] , wherein the adhesive contains low or no VOCs and has at least 24 wt% of a bio- based material. 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. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control. The descriptions of the various embodiments of the present invention have been presented for purposes of illustration, but are not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others or ordinary skill in the art to understand the embodiments disclosed herein. Except where expressly noted, trademarks are shown in upper case. Unless stated otherwise, all percentages, parts, ratios, etc., are by weight. When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values recited when defining a range. Further, where a numerical limit or range is stated herein, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out. Further, unless otherwise explicitly stated to the contrary, when one or multiple ranges or lists of items are provided, this is to be understood as explicitly disclosing any Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 single stated value or item in such range or list, and any combination thereof with any other individual value or item in the same or any other list. When the term “about” is used, it is used to mean a certain effect or result can be obtained within a certain tolerance, and the skilled person knows how to obtain the tolerance. When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim, closing the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The transitional phrase "consisting essentially of" limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention. A “consisting essentially of” claim occupies a middle ground between closed claims that are written in a “consisting of” format and fully open claims that are drafted in a “comprising” format. Optional additives as defined herein, at a level that is appropriate for such additives, and minor impurities are not excluded from a composition by the term “consisting essentially of”. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 As used herein, an "embodiment" means that a particular feature, structure or characteristic is included in at least one or more manifestations, examples, or implementations of this invention. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art. Combinations of features of different embodiments are all meant to be within the scope of the invention, without the need for explicitly describing every possible permutation by example. Thus, any of the claimed embodiments can be used in any combination. Further, unless expressly stated to the contrary, “and / or” refers to an inclusive and not to an exclusive. Thus, “and / or” should be understood to mean “either or both” of the elements so conjoined, e.g., elements that are conjunctively present in some cases and disjunctively present in other cases. For example, a condition A and / or B, is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). The use of "a" or "an" to describe the various elements and components herein is merely for convenience and to give a general sense of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. Similarly, the adjective “another,” when used to introduce an element, is intended to mean one or more elements. The terms “including” and “having” are intended to be inclusive such that there may be additional elements other than the listed elements. The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description. Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 As used herein, the phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials. The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description. Although this invention has been described with a certain degree of particularity, it is to be understood that the present disclosure has been made only by way of illustration and that numerous changes in the details of construction and arrangement of parts may be resorted to without departing from the spirit and the scope of the invention. The above description is presented to enable a person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other 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. Numerous modifications and variations on the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the accompanying claims, the invention may be practiced otherwise than as specifically described herein.

Claims

Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 CLAIMS What we claim is 1. A process for preparing a non-isocyanate polyurethane (NIPU) comprising: a) Dissolving a hydroxyl source in a solvent; b) Adding a carbonyl source and a catalyst to the solution resulting in (a) to facilitate a transesterification reaction between the hydroxyl source and the carbonyl source; c) Heating the mixture from (b) to a temperature between 60-120°C and stirring for a period of 1-24 hours; d) Adding a hardening agent to the mixture resulting from (c) and stirring for an additional period of 1-24 hours at room temperature to produce an NIPU; and e) Optionally, isolating and / or purifying the resulting NIPU.

2. The method of claim 1, wherein the hydroxyl source is a phenolic compound.

3. The method of claim 2, wherein the phenolic compound is a tannin compound.

4. The method of claim 2, wherein the phenolic compound is selected from the group consisting of tannic acid, gallic acid, pyrogallol, catechol, resorcinol, and a condensed tannin.

5. The method of claim 1, wherein the carbonyl source is a carbonate or a carbonate precursor.

6. The method of claim 5, wherein the carbonyl source is a dialkyl carbonates having 1 to 6 carbon atoms.

7. The method of claim 1, wherein the solvent in (a) is water or a C1 to C6 alkanol.Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 8. The method of claim 1, wherein the catalyst for the transesterification reaction in (b) is a Lewis acid.

9. The method of claim 1, wherein the catalyst for the transesterification reaction in (b) is an organotin compound, a metal oxide, a metal carboxylates, a mercaptides oxide, or a combination thereof.

10. The method of claim 1, wherein the hydroxyl source and the carbonyl source are provided in a molar ratio in a range from 4:1 to 1:

4.

11. The method of claim 1, wherein the catalyst is present in the range of from 0.001 to 2.5 mol% based on total moles of hydroxyl groups present in the hydroxyl source.

12. The method of claim 1, wherein the hardening agent is a biobased hardening agent.

13. The method of claim 1, wherein the hardening agent is a phenylalkamine or a phenylalkamide.

14. The method of claim 1, further comprising adding a cyclic alkylene carbonate during (d).

15. The method of claim 1, comprising: a) Dissolving a phenolic compound in a water; b) Adding a dimethyl carbonate and a dibutyltin dilaurate to the solution resulting in (a) to facilitate a transesterification reaction between the phenolic compound and dimethyl carbonate; c) Heating the mixture from (b) to a temperature between 60-120°C and stirring for a period of 1-24 hours;Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 d) Adding a phenylalkamine or phenylalkamide hardening agent to the mixture resulting from (c) and stirring for an additional period of 1-24 hours at room temperature to produce an NIPU; and e) Optionally, isolating and / or purifying the resulting NIPU.

16. A method of coating a surface of a material with a coating composition, comprising: applying a coating composition comprising an NIPU prepared by the method of claim 1 to the surface of a materials selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, and textiles; and allowing the solvent to evaporate.

17. A coated material, wherein said material has a coating thereon wherein the coating comprises an NIPU prepared by the method of claim 1.

18. A method of adhering a surface of a first material to a surface of second material by: (1) applying a layer of an adhesive composition comprising an NIPU prepared by the method of claim 1 to a surface of one or both materials, wherein the materials may be the same or different materials and is selected from the group consisting of ceramic, glass, concrete, wood, metal, galvanized steel, ungalvanized steel, tile, and textiles, and (2) contacting the surface of the first material to the surface of the second surface; and (3) allowing the adhesive composition to harden and the solvent to evaporate.

19. A material construct wherein a surface of a first material is affixed to a surface of second material by an adhesive which comprises an NIPU prepared by the method of claim 1,Attorney Docket No.: BIOB-009 / 01WO 40787 / 57 wherein the adhesive contains low or no VOCs and has at least 24 wt% of a bio-based material.

Images