Vinyl-terminated polyaspartic-polyurea hybrid dispersion and its application in adhesives and coatings

Abstract

The present invention relates to a stable vinyl-terminated polyaspartic-polyurea hybrid dispersion for its application in adhesives and coatings. Herein, the vinyl-terminated polyaspartic-polyurea hybrid dispersion is further modified with a monomeric component, such as an acrylic moiety and vinyl acetate monomer. The dispersion demonstrates excellent water resistance and stability. The developed dispersions are suitable for use in coatings, paints, adhesives, sealants, and inks, and are applied onto various substrates, including cementitious materials, metals, glass, plastics, carpet, wood, textiles, ceramics, and composites.

Description

[0001] VINYL-TERMINATED POLYASPARTIC-POLYUREA HYBRID DISPERSION AND ITS APPLICATION IN ADHESIVES AND COATINGS

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS AND PRIORITY

[0003] The present application claims priority from the Indian provisional patent application number 202421045128 filed on 11thJune 2024, the details of which are incorporated herein by a reference.

[0004] TECHNICAL FIELD

[0005] The present invention described herein, in general, relates to a composition for polyaspartic- polyurea dispersion. More particularly, it relates to the vinyl terminated polyaspartic-polyurea hybrid dispersion comprising a vinyl-terminated polyurea polymer modified by colloidal / non- colloidal grafting of vinyl components and other monomers.

[0006] BACKGROUND

[0007] In general, synthetic polymer dispersions are prepared by polymerizing unsaturated monomeric materials in a liquid medium, usually water, under the influence of free radicals. At the end of the polymerization stage, such dispersions typically contain volatile organic compounds that result from incomplete monomer conversion, impurities of raw materials, and undesirable by-products formed during the polymerization reaction.

[0008] These volatile organic compounds (VOCs), also known as organic chemicals, adversely affect the environment and human health. Moreover, such VOCs also cause damage to materials prepared by the dispersion as a consequence of their oxidizing or corrosive properties.

[0009] Thus, various federal and state agencies have established regulations requiring a reduction in the volatile organic chemicals (VOCs) released from surface coatings or paints. Such regulations concerning VOC content vary depending on the region or state to combat ground-level air pollution and to minimize, monitor, and control the effects of VOCs.

[0010] Also, as environmental awareness and concerns of consumers have grown, and governmental agencies have imposed stricter regulations regarding the release into the atmosphere of VOCs, the researchers have sought means for reducing the VOC content of their products. It would therefore be desirable to provide dispersions that have a low or reduced VOC content or a method to reduce the overall VOC content of the prepared dispersions. Thus, efficient technologies are necessary to reduce VOC concentrations by carefully designing the dispersion that is able to chelate, adsorb, or chemically modify them, while also considering the efficiency, reuse, and costs of obtaining.

[0011] In the state of the art, polyurea is modified with functional groups such as amine groups or vinyl monomers to enhance its performance and versatility, addressing specific application requirements and challenges. Through targeted modifications, the polyurea formulation achieves improved properties, ensuring its suitability for a wide range of applications. However, such modifications are either complex and develop an unstable dispersion with high VOC concentration or demonstrate diminished properties such as adhesion, flexibility, UV stability, water resistance, and chemical resistance.

[0012] Therefore, there is a long-felt need to modify the existing polyurea dispersion to obtain a stable dispersion with minimal or zero VOC content and an efficient process to minimize the volatile organic compound (VOC) content of the modified polyurea dispersion while enhancing the properties of the dispersion.

[0013] SUMMARY

[0014] This summary is provided to introduce concepts related to a polyaspartic-polyurea hybrid dispersion. This summary is not intended to identify essential features of the presently claimed invention, nor it is intended for use in determining or limiting the scope of the disclosed invention.

[0015] In accordance with one or more aspects of the present invention, a vinyl-terminated polyaspartic- polyurea hybrid dispersion is described herein.

[0016] In an aspect of the present invention, there is provided a vinyl-terminated polyaspartic polyurea hybrid dispersion. The vinyl-terminated polyaspartic polyurea hybrid dispersion comprises a vinyl-terminated polyurea polymer dispersed therein.

[0017] In one embodiment of the present invention, the vinyl -terminated polyurea polymer is a reaction product of one or more reactants comprising i) at least one polyol moiety, ii) at least one isocyanate component, iii) at least one polyaspartic component, iv) at least one emulsifier, and v) a hydroxyl vinyl-based monomer.

[0018] In another embodiment of the present invention, the hydroxyl vinyl-based monomer is selected a group consisting of 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 4-hydroxybutyl acrylate, and polyethylene glycol (meth)acrylates, glycerol dimethacrylate (GDMA). In another aspect of the present invention, there is provided an acryl-polyaspartic polyurea hybrid emulsion comprising an acryl-modified polyurea polymer. The acryl-modified polyurea polymer is a reaction product of i) at least one acrylic moiety, ii) the vinyl-terminated polyaspartic polyurea hybrid dispersion, and iii) at least one surfactant.

[0019] In yet another aspect of the present invention, there is provided a colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion. The colloid stabilized polyvinyl acetate-polyurea hybrid dispersion comprises a colloid stabilized polyvinyl acetate-polyurea polymer dispersed therein. The colloid stabilized polyurea polymer is a reaction product of i) at least one colloid component, ii) the vinyl-terminated polyaspartic polyurea hybrid dispersion, and iii) a vinyl acetate monomer.

[0020] In still another aspect of the present invention, there is provided a composition comprising the vinyl-terminated polyaspartic polyurea hybrid dispersion of the present invention. The composition is selected from a coating composition, a paint, an adhesive, a sealant, and an ink.

[0021] In yet another aspect of the present invention, an article comprising a substrate and the coating composition is disclosed.

[0022] DETAILED DESCRIPTION

[0023] Reference throughout the specification to “various embodiments,” “some embodiments,” “one embodiment,” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, appearances of the phrases “in various embodiments,” “in some embodiments,” “in one embodiment,” or “in an embodiment” in places throughout the specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner in one or more embodiments.

[0024] The words "comprising," "having," "containing," and "including," and other forms thereof, are intended to be equivalent in meaning and be open ended in that an item or items following any one of these words is not meant to be an exhaustive listing of such item or items or meant to be limited to only the listed item or items. It must also be noted that, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Although any methods similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, the exemplary methods are described. The disclosed embodiments are merely exemplary of the present invention, which may be embodied in various forms.

[0025] Various modifications to the embodiment may be readily apparent to those skilled in the art, and the generic principles herein may be applied to other embodiments. However, one of ordinary skill in the art may readily recognize that the present invention is not intended to be limited to the embodiments illustrated but is to be accorded the widest scope consistent with the principles and features described herein.

[0026] In an aspect of the invention, there is provided a vinyl-terminated polyaspartic polyurea hybrid dispersion. The vinyl-terminated polyaspartic polyurea hybrid dispersion is interchangeably referred to as ‘the dispersion’. The vinyl -terminated polyaspartic polyurea hybrid dispersion is obtained by colloidal and non-colloidal grafting of the polyaspartic-polyurea polymer with vinylcontaining monomers such as vinyl acetate, acrylic moiety, and hydroxyl vinyl-containing monomer.

[0027] The dispersion is specifically formulated for use in wood adhesives and exterior glass sealants. The vinyl grafting results in enhanced water-resistant D4-grade wood adhesives and high-initial- tack glass sealants. Further, the dispersion is also suitable for general paints and coatings applications, offering improved stain resistance, high gloss, and even anticorrosive properties for applications on walls, wood, and glass surfaces.

[0028] In an aspect of the present invention, a vinyl-terminated polyaspartic polyurea hybrid dispersion is disclosed. The vinyl-terminated polyaspartic polyurea hybrid dispersion comprises a vinyl- terminated polyurea polymer dispersed therein. Herein, the vinyl-terminated polyurea polymer is a reaction product of one or more reactants comprising at least one polyol moiety, at least one isocyanate component, at least one polyaspartic component, at least one emulsifier, and a hydroxyl vinyl-based monomer.

[0029] In one embodiment, the reactant for obtaining vinyl -terminated polyurea polymer is at least one polyol moiety.

[0030] For the purposes of the present invention, the term "at least one polyol moiety" refers to either a single monomeric polyol or a mixture thereof.

[0031] Herein, the at least one polyol include, but is not limited to, polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), and poly(tetramethylene ether) glycol (PTMEG); polyester polyols including polycaprolactone polyol (PCL), polybutylene adipate glycol (PBA), and polyethylene adipate glycol (PEA); polycarbonate polyols; polyurethane diols; tetrahydrofuran polyols; acrylic polyols; polyester / polycarbonate blends; aromatic polyols derived from toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI); renewable polyols such as soy-based and castor oil-based polyols; hydroxyl-terminated polybutadiene (HTPB); acrylonitrile butadiene polyols (NBP); or combinations thereof.

[0032] In a related embodiment, the polyol moiety, having at least two hydroxyl groups, include but is not limited to ethylene glycol, 1,2-propanediol, 1,3 -propanediol, 1,1 -dimethylethane- 1,2-diol, 2- butyl-2-ethyl- 1,3 -propanediol, 2-ethyl- 1,3 -propanediol, 2-methyl-l,3-propanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, various butanediols (1,2-, 1,3-, or 1,4-), 1,6-hexanediol, 1,10-decanediol, bis(4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, cyclohexanediols (1,2-, 1,3-, or 1,4-), cyclooctanediol, norbornanediol, pinanediol, decalindiol, 2- ethy 1-1, 3 -hexanediol, 2,4-diethyloctan-l,3-diol, hydroquinone, bisphenols A, F, B, and S, 2,2- bis(4-hydroxycyclohexyl)propane, cyclohexanedimethanols (1,1-, 1,2-, 1,3-, and 1,4-), trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and di glycerol.

[0033] In a preferred embodiment, the at least one polyol moiety is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyisobutylene glycol, polytetrahydrofuran diol, polycarbonate diol, polycaprolactone triol, polyethylene adipate diol, poly-1, 4-butanediol adipate diol, and poly-hexanediol adipate diol.

[0034] In another embodiment, the reactant for obtaining vinyl -terminated polyurea polymer is at least one isocyanate moiety.

[0035] For the purposes of the present invention, the term ‘at least one isocyanate moiety’ refers to either monomeric isocyanate, aliphatic diisocyanate, aromatic diisocyanate, and or a poly-isocyanate or a mixture thereof.

[0036] In a related embodiment, the isocyanate moiety is a polyisocyanate selected from but not limited to polyisocyanate of hexamethylene- 1,6-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4’-dicychohexylemethane diisocyanate, 2,2-diphenylmethane diisocyanate, 4,4- diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,2- phenylene diisocyanate , 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, triphenyl methane-4,4’,4”-triisocyanate, naphthylene-l,5-diisocyanate, polyphenyl polymethylene polyisocyanate, 1,2-xylylene diisocyanate, 1,3- xylylene diisocyanate, 1,4-xylylene diisocyanate, m-tetramethylxylyene diisocyanate (TMXDI), tetramethylene 1,4-diisocyanate, pentamethylene

[0037] 1.5 -diisocyanate, decamethylene diisocyanate, 1,12-dodecane diisocyanate, 2-methyl-l,5- pentamethylene diisocyanate, cyclobutene- 1,3 -diisocyanate, 1,2-cyclohexane diisocyanate, 1,3- cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-methylcyclohexane diisocyanate,

[0038] 2.6-methylcyclohexane diisocyanate, 4,4’-dicyclohexyldiisocyanate, 2,4’- dicyclohexyldiisocyanate, bis(isocyanatomethyl)-cyclohexane diisocyanate, isophorone diisocyanate or a mixture thereof.

[0039] In a related embodiment, the aliphatic polyisocyanate is selected from but not limited to hexamethylene-l,6-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4’- dicychohexylemethane diisocyanate, tetramethylene 1,4-diisocyanate, pentamethylene 1,5- diisocyanate, hexamethylene 1,6-diisocyanate, decamethylene diisocyanate, 1,12-dodecane diisocyanate, 2-methyl-l,5-pentamethylene diisocyanate, cyclobutene- 1, 3 -diisocyanate, 1,2- cyclohexane diisocyanate, 1,3 -cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 2,4- methylcyclohexane diisocyanate, 2,6-methylcyclohexane diisocyanate, 4,4’- dicyclohexyldiisocyanate, bis(isocyanatomethyl)-cyclohexane diisocyanate, 2,4’- dicyclohexyldiisocyanates, or bis(isocyanatomethyl)-cyclohexane diisocyanate.

[0040] In a related embodiment, the aromatic polyisocyanate is selected from but not limited to 2,2- diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, triphenyl methane-4,4’,4”-triisocyanate, naphthylene-l,5-diisocyanate, polyphenyl polymethylene polyisocyanate, 1,2- xylylene diisocyanate, 1,3- xylylene diisocyanate, 1,4- xylylene diisocyanate, m-tetramethylxylyene diisocyanate (TMXDI) or mixtures thereof.

[0041] In a preferred embodiment, the isocyanate moiety is a diisocyanate having 4 to 20 carbon atoms. Examples of typical diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene 1,5 -diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, and like.

[0042] Herein, the vinyl-terminated polyaspartic polyurea hybrid dispersion has an NCO / OH ratio in the range of 1.2 to 2.0.

[0043] In yet another embodiment, the reactant for obtaining vinyl -terminated polyurea polymer is at least one polyaspartic component. The at least one polyaspartic component is a polyaspartic ester. Herein, the modification of polyurea with at least one polyaspartic component results in enhancement of the chemical and water resistance of the dispersion.

[0044] The polyaspartic esters are secondary slow-reacting polyamines due to their sterically hindered environment of the secondary amino functional group. In one embodiment, the polyaspartic ester is selected from cycloaliphatic polyaspartic ester, aliphatic polyaspartic ester, diethylenetriamine polyaspartic ester, tetrahydrofurfuryl polyaspartic ester, isophorone polyaspartic ester, bi s(aminomethyl)poly aspartic ester, methylhexyl poly aspartic ester.

[0045] In a preferred embodiment, the polyaspartic ester is a reaction product of dialkyl maleate and diamine compound. The dialkyl maleate herein is at least one selected from a group consisting of dimethyl maleate, diethyl maleate, dibutyl maleate, diisobutyl maleate, dipropyl maleate, diisopropyl maleate, dihexyl maleate, dioctyl maleate, diisooctyl maleate, and dicyclohexyl maleate. Further, the diamine compound is at least one selected from a group consisting of isophorone diamine, ethylene diamine, diaminobutane 1,6-hexam ethylene diamine, 2- methylpentane- 1,5-diamine, and poly etheramines.

[0046] In still another embodiment, the reactant for obtaining vinyl -terminated polyurea polymer is at least one emulsifier. Herein the at least one emulsifier includes, but is not limited to, dimethylol propionic acid, dimethylol butanoic acid, citric acid, tartaric acid, diphenolic acid, hydroxymethylpropionic acid, and trimethylolpropionic acid and cyclic carboxylic acids, e.g., 5- hydroxymethyl furanoic acid.

[0047] In a related embodiment, the at least one emulsifier forms a part of the backbone structure of the polymer and provides long-term stability to the polymer by reducing interparticle forces and preventing aggregation and more uniform distribution of the polymer throughout the dispersion. In still yet another embodiment, the reactant for obtaining vinyl-terminated polyurea polymer is the hydroxyl vinyl-based monomer. Herein, the hydroxyl vinyl-based monomer is selected from the group consisting of 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 4-hydroxybutyl acrylate, and polyethylene glycol (meth)acrylates, glycerol dimethacrylate (GDMA). Herein, the hydroxyl vinyl-based monomer is attached at the terminal end of the polymer.

[0048] In yet another embodiment, the vinyl-terminated polyurea polymer is obtained in the presence of at least one additive selected from a group consisting of at least one neutralizing agent, at least one defoamer, at least one inhibitor, and a combination thereof.

[0049] Herein, the at least one neutralizing agent is a tertiary amine comprising at least one of a triethanolamine (TEA), a triethylamine, an aminomethyl propanol (AMP®-95), di-isopropyl ethylamine, a tromethamine (Tris Amino®), and tetrakis-2-hydroxypropyl ethylenediamine (a Neutrol® TE), dimethylethanolamine, diethylethanolamine, or ethylenediamine. Here, the neutralizing agent reacts with the excess isocyanate group present at the terminal end of the polyurea prepolymer, as the unwanted isocyanate groups lead to unwanted reactions or cause issues in the final polymer.

[0050] Thus, the neutralization step is carried out to achieve the desired reduced NCO content in the prepolymer. The desired reduced NCO content is important for controlling the curing or crosslinking reactions and to ensure that the prepolymer is well-suited for subsequent processing and application.

[0051] Herein, the at least one inhibitor is selected from tolu-hydroquinone or hydroquinone. Herein, the chain growth of vinyl-terminated polyurea polymer is inhibited by adding inhibitors such as tolu- hydroquinone / hydroquinone. The inhibitors herein quench the free radical, which inhibits the initiation of radical polymerization. However, excessive amounts or prolonged exposure to inhibitors adversely affect the polymerization process or the final properties of the polymer. Thus, the concentration of the inhibitor depends on the monomers involved and the desired properties of the final product.

[0052] In a related aspect of the present invention, there is provided a method for the preparation of the vinyl-terminated polyurea polymer.

[0053] The method for obtaining the vinyl-terminated polyurea polymer comprises a step of reacting the at least one polyol moiety, the at least one isocyanate component, and the at least one emulsifier to form an isocyanate functional prepolymer. The method includes a step of neutralizing the isocyanate functional prepolymer with at least one neutralizing agent to form a neutralized prepolymer. Furthermore, the method includes a step of reacting the neutralized prepolymer with the at least one polyaspartic component to obtain a polyaspartic polyurea polymer. Further, the method includes a step of treating the polyaspartic polyurea polymer with the hydroxyl vinylbased monomer to obtain the vinyl-terminated polyurea polymer.

[0054] Herein, the developed vinyl -terminated polyurea polymer is one component in nature.

[0055] In another related aspect of the present invention, there is provided a method for preparing the vinyl-terminated polyaspartic polyurea hybrid dispersion from the vinyl-terminated polyurea polymer.

[0056] Herein, the method includes a step of dispersing the vinyl-terminated polyurea polymer in a solvent to obtain the vinyl-terminated polyaspartic polyurea hybrid dispersion. The solvent used herein is selected from a group comprising organic solvents, aqueous solvents, or mixtures thereof, chosen based on their compatibility with the polymeric components and desired application performance. The vinyl group in the polymer ensures a uniform distribution of the polymer in the solvent to obtain a stable dispersion.

[0057] In a related embodiment, the method includes a step of curing the vinyl -terminated polyurea polymer in UV light with subsequent addition of photo-initiator to obtain the UV curable vinyl- terminated polyurea polymer. Herein, the photo-initiators include, but are not limited to, benzoin methyl ether, benzoin ethyl ether, and benzoin isobutyl ether, wherein the photo-initiators are activated by exposure to ultraviolet (UV) light, initiating polymerization.

[0058] Depending on the requirements of the dispersion application, the vinyl -terminated polyurea polymer is tailored with the vinyl -containing monomeric component to ensure that the desired properties are achieved in accordance with the intended end-use, such as chemical and water resistance of the dispersion when applied on a substrate in the form of an adhesive or coating.

[0059] Herein, the dispersion has a solid content of 30 to 50%. Herein, the dispersion a particle size in a range of 50 nm to 250 nm; a viscosity in a range of 300 to 1500, measured by Brookfield viscometer at 25°C; and a pH in a range of 7.5 to 8.5, measured by pH meter at 25°C. In another aspect of the invention, an acryl-polyaspartic polyurea hybrid emulsion is disclosed. The acryl-polyaspartic polyurea hybrid emulsion comprises an acryl-modified polyurea polymer. The acryl-modified polyurea polymer is a reaction product of at least one acrylic moiety, the vinyl- terminated polyaspartic polyurea hybrid dispersion, and at least one surfactant.

[0060] In an embodiment, a reactant for obtaining the acryl-polyaspartic polyurea polymer is at least one acrylic moiety. The at least one acrylic moiety is selected from a group comprising methyl methacrylate, ethyl methacrylate, diethylene glycol dimethacrylate, butyl methacrylate, and any combination thereof.

[0061] In another embodiment, the reactant for obtaining the acryl-modified polyurea polymer is the vinyl-terminated polyaspartic polyurea hybrid dispersion. Herein, the vinyl-terminated polyurea polymer is a reaction product of one or more reactants comprising at least one polyol moiety, at least one isocyanate component, at least one polyaspartic component, at least one emulsifier, and a hydroxyl vinyl-based monomer.

[0062] In yet another embodiment, the reactant for obtaining the acryl-modified polyurea polymer is at least one surfactant. Herein, the at least one surfactant is selected from an anionic or non-ionic surfactant. The surfactant is selected from a group comprising sodium lauryl sulfate, sodium lauryl ether sulfate, linear alkylbenzene sulfonate, alpha-olefin sulfonate, sodium cocoyl isethionate, sodium lauroyl sarcosinate, disodium lauryl sulfosuccinate, sodium cocoyl glycinate, sodium methyl cocoyl taurate, alkyl polyglycosides, coco glucoside, lauryl glucoside, alcohol ethoxylates, polyethylene glycol, sucrose esters, and a combination thereof.

[0063] In yet another embodiment, the acryl-polyaspartic polyurea hybrid emulsion is obtained in the presence of at least one additive selected from a group consisting of at least one defoamer, and at least one radical initiator.

[0064] Herein, the at least one radical initiator is selected from a group consisting of alkyl peroxides, ammonium persulfate, potassium persulfate, sodium persulfate, and hydrogen peroxide azo compounds. The radical initiator decomposes upon heating or during a redox reaction to generate free radicals, which are effective in initiating polymerization reactions for acryl-polyaspartic polyurea polymer.

[0065] In a related aspect of the present invention, there is provided a method for the preparation of the acryl-polyaspartic polyurea hybrid emulsion.

[0066] Herein, the method includes a step of diluting the vinyl -terminated polyaspartic polyurea hybrid dispersion, followed by the addition of surfactant to obtain a pre-emulsion. The method further comprises a step of grafting the pre-emulsion with the at least one acrylic moiety to obtain the acryl-polyaspartic polyurea hybrid emulsion. Herein, the acryl-polyaspartic polyurea hybrid emulsion is obtained via polymerization that occurs through a free radical growth mechanism in which the initiator generates free radicals, which react with successive polymer and one acrylic moiety at an active chain end. Herein, the obtained polymer particles are initially submicron in size, are stabilized by the surfactants.

[0067] In a preferred embodiment, the method for obtaining the acryl-polyaspartic polyurea hybrid emulsion is carried out in two stages. The vinyl -terminated polyaspartic polyurea hybrid dispersion is synthesized by step-growth polymerization, and then the chains of the at least one acrylic moiety are grown over the vinyl terminations via free radical polymerization to obtain the vinyl - terminated polyurea polymer.

[0068] In a more preferred embodiment, the method includes a step of adding a predefined combination of water and surfactant to the vinyl-terminated polyaspartic polyurea hybrid dispersion to obtain a pre-emulsion. Further, the method includes a step of polymerization via grafting the pre-emulsion with the at least one acrylic moiety in the presence of a radical initiator to obtain the acryl- polyaspartic polyurea hybrid emulsion.

[0069] Herein, the dispersion has a solid content of 30 to 50%. Herein, the dispersion a particle size in a range of 50 nm to 250 nm. The viscosity is in a range of 300 to 1500, measured by Brookfield viscometer at 25°C, and a pH is in a range of 7.5 to 8.5, measured by pH meter at 25°C.

[0070] In yet another aspect of the invention, a colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion is disclosed. The colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion comprises a colloid-stabilized polyvinyl acetate-polyurea polymer dispersed therein. The colloid- stabilized polyvinyl acetate-polyurea polymer is a reaction product of at least one colloid component, the vinyl -terminated polyaspartic polyurea hybrid dispersion, and a vinyl acetate monomer.

[0071] In an embodiment, the reactant for obtaining colloid-stabilized polyvinyl acetate-polyurea polymer is at least one colloid component. Preferably, the at least one colloid component is selected from a group comprising polyvinyl alcohol, alkyl hydroxy ethyl cellulose, and glycols. Preferably, the at least one colloid component is prepared by solubilizing the polyvinyl alcohol in water and acts as an emulsifier.

[0072] In another embodiment, the reactant for obtaining the colloid-stabilized polyvinyl acetate-polyurea polymer is the vinyl-terminated polyaspartic polyurea hybrid dispersion. Herein, the vinyl- terminated polyurea polymer is a reaction product of one or more reactants comprising at least one polyol moiety, at least one isocyanate component, at least one polyaspartic component, at least one emulsifier, and a hydroxyl vinyl-based monomer.

[0073] In another embodiment, the reactant for obtaining the colloid-stabilized polyvinyl acetate-polyurea polymer is at least one vinyl acetate monomer. Herein, the at least one vinyl acetate monomer is selected from a group of vinyl esters of alkane monocarboxylic acids having two to five carbon atoms.

[0074] In yet another embodiment, the colloid stabilized polyvinyl acetate-polyurea hybrid dispersion is obtained in the presence of at least one additive selected from a group consisting of a cross-linking agent, a defoamer, a radical initiator, a surface-active agent, and an anti-microbial agent.

[0075] Herein, the cross-linking agents include but are not limited to multifunctional epoxides, polyfunctional aziridines, and di-functional isocyanates, and the alike. The cross-linking agents are typically multi-functional monomers that can react with vinyl groups on the polymer chains, leading to the formation of cross-links.

[0076] The radical initiators used herein include, but are not limited to, alkyl peroxides, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, and azo compounds such as azobisisobutyronitrile. The radical initiator decomposes upon heating or during a redox reaction to generate free radicals, which are effective in initiating polymerization reactions for colloid- stabilized polyvinyl acetate-polyurea polymer.

[0077] In a related aspect of the present invention, there is provided a method for the preparation of the colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion. The method includes a step of mixing at least one colloid component and the vinyl -terminated polyaspartic polyurea hybrid dispersion, followed by the addition of radical initiator, crosslinker, and surfactant to obtain a premix. Furthermore, the method includes a step of adding vinyl acetate monomer to the premix in the presence of radical initiator, surfactant, and antimicrobial agent to obtain the colloid- stabilized polyvinyl acetate-polyurea hybrid dispersion.

[0078] In still another aspect of the present invention, there is provided a composition comprising the vinyl-terminated polyaspartic polyurea hybrid dispersion.

[0079] In a preferred embodiment, the composition is an ink composition.

[0080] In a preferred embodiment, the composition is an adhesive composition.

[0081] In a preferred embodiment, the composition is a paint composition.

[0082] In a preferred embodiment, the composition is a coating composition. The coating composition comprises the vinyl-terminated polyaspartic polyurea hybrid dispersion and at least one additive. In another aspect of the present invention, there is provided an article. The article comprises a substrate and a coating composition applied on the substrate. The substrate is selected from the group consisting of cementitious materials, metals, glass, plastics, carpet, wood, textiles, ceramics, and composites.

[0083] Herein, the unique combination of polyol moiety, polyaspartic moiety, isocyanate component, and a vinyl monomer imparts required properties in the water resistance and chemical barrier coating composition, as well as anticorrosive paints.

[0084] Herein, the vinyl-terminated polyaspartic polyurea hybrid dispersion exhibits superior adhesive properties when used with wood substrates due to the presence of polyaspartic polyurea in the polymer matrix. Furthermore, when employed as a sealant, the dispersion demonstrates excellent tear strength and initial tack (grab) characteristics, making it highly effective in demanding applications.

[0085] Moreover, the disclosure relates to advantages obtained by implementing the method for preparing the dispersion are that the organic solvent is recovered from the dispersion, resulting in the dispersion having minimal or zero VOC content. Thus, the method disclosed in the present application is a sustainable approach for preparing the dispersion.

[0086] The present invention is illustrated in detail by non-limiting working examples which follow. The non-limiting and non-exhaustive examples are intended to further describe various non-limiting and non-exhaustive embodiments without restricting the scope of the embodiments described in the specification. More particularly, the test methods specified hereinafter are part of the general disclosure of the application and are not restricted to the specific working examples.

[0087] EXAMPLE

[0088] The following examples are provided to further illustrate the present invention and are not intended to limit its scope in any way. All weight percentages (%wt) or total weights of the materials used are calculated on an equivalent basis, unless otherwise specified. The equivalence and functional determinations were carried out using analytical methods at 25 °C.

[0089] Herein, the percentage (%) solid content was determined as per WI4001 oven heating at 105 °C for 90 min. Viscosities were measured using a Brookfield viscometer at 25 °C. The pH of the dispersions was measured using a calibrated pH meter at 25 °C. Particle size measurements were determined using the Zeta sizer instrument.

[0090] GLOSSARY

[0091] ETERNACOLL® UHIOO-Poly carbonate diol (Eternal Materials Co.)

[0092] Desmophen® NH 1420- Polyaspartic ester resin (Covestro / Bayer)

[0093] BYK®-024 - Silicone-based defoamer (BYK-Chemie)

[0094] PolyTHF® 2000 - Polytertahydrofuran polyol supplied by BASF chemicals, Average Mol wt. of 2000, Hydroxyl Value of 53-56 mg KOH / gm

[0095] Rhodoline® Wa 40 - Wetting agent / surf actant (Solvay / Rhodia)

[0096] Rhodapex® ESB 28 - Sodium lauryl ether sulfate (SLES), surfactant (Solvay / Rhodia)

[0097] BP17A - Likely a resin, binder, or plasticizer Foamasters® - Defoamer / anti-foam additive (e.g., Munzing)

[0098] PROXEL™ GX - Broad-spectrum biocide (LANXESS or Arch Chemicals)

[0099] Example 1: Synthesis of vinyl-terminated polyaspartic polyurea hybrid dispersion A

[0100] In a dry four-neck glass reactor, 1013.25 g PolyTHF®2000, 64.5 g dimethylolpropionic acid were charged and heated to 90 °C, followed by applying a vacuum to remove the moisture less than 0.1%. The temperature was then brought to 50°C under a nitrogen atmosphere, and 0.75 g of dibutyltin dilaurate. After 15 mins mixing, 422.25 g of isophorone diisocyanate were charged over the 15 minutes, followed by rinsing with 75 g of acetone to obtain a prepolymer mixture. The temperature of 80 to 85°C was maintained.

[0101] The prepolymer mixture was then neutralized with 43.75 g of triethylamine over 30 mins digestion. The neutralized prepolymer was extended with a mixture of 335 g Desm ophen® NH1420 and 600 g acetone. The complete extension was held for a further 60 mins. 0.45 g of monomethyl ether of hydroquinone was added and allowed to mix for the next 10 mins. Further, 46.41 g of 2- hydroxyethyl methacrylate was added dropwise over 30 mins and held for the next 45 mins for complete reaction.

[0102] The resultant mixture is then transferred to a dispersion vessel and mixed at 1000-1200 rpm. A mixture of 2 g BYK®-024 and 3350 g deionized water was added to the prepolymer over 15 mins of time and digested for the next 30 mins. A dispersion was then heated to 55°C, and acetone was removed under vacuum to get the volume parameters.

[0103] A bluish-white, stable dispersion was obtained, characterized by a solid content of 34.5%, a pH of 7.51, and a viscosity of 1200 cPs, as measured using a Brookfield viscometer at 25 °C. The mean particle size was determined to be 58 nm using a Zetasizer, and the average molecular weight of the polymer in the dispersion was approximately 190376. These parameters indicate excellent dispersion stability, a uniform particle size distribution, and favorable rheological behavior.

[0104] Infrared (IR) spectroscopy confirmed the presence of an unsaturation peak at 1637 cm While initially masked by water in the dispersion, this peak became clearly visible upon drying, with no change observed in the intensity of the NH bond peak at 3337 cm Upon complete curing, the unsaturation peak disappeared, indicating successful crosslinking.

[0105] Proton nuclear magnetic resonance (’H-NMR) analysis was conducted to quantify the vinyl content. Resonances at 5 6.13 and 5 5.56 ppm were assigned to vinyl protons. Although the expected doublet of doublets appeared as broad signals — likely due to the limited resolution of the 300 MHz instrument — the data were sufficient for quantification. The vinyl content, calculated based on the integration of these signals relative to the three protons of the isophorone diisocyanate unit at 5 0.93 ppm, was found to be 3.84%. Furthermore, the dispersion exhibits a breaking load (N) of 9.3 and a % breaking elongation of 424.

[0106] Example 2: Synthesis of vinyl-terminated polyaspartic polyurea hybrid dispersion B

[0107] In a dry four-neck glass reactor, 696 g PolyTHF®2000, 36.1 g dimethylolpropionic acid were charged and heated to 90°C, applying a vacuum to remove the moisture level less than 0.1%. The temperature was then brought to 50 °C under a nitrogen atmosphere, and 0.5 g of dibutyltin dilaurate was added. After 15 mins mixing, 267.9 g of isophorone diisocyanate were charged over the 15 minutes, followed by rinsing with 60 g of Acetone to obtain a prepolymer mixture. The temperature of 80 to 85°C was maintained.

[0108] The prepolymer mixture was then neutralized with 24.5 g of triethylamine over 30 mins digestion. The neutralized prepolymer was extended with a mixture of 130 g Desmophen® NH1420 and 428 g acetone. The complete extension was held for a further 60 mins. Further, 0.3 g of monomethyl ether of hydroquinone was added and allowed to mix for the next 10 mins. 60.71 g of 2- hydroxyethyl methacrylate was added dropwise over 30 mins and held for the next 45 mins for complete reaction.

[0109] The resultant mixture is then transferred to a dispersion vessel and mixed at 1000-1200 rpm. A mixture of 1 g BYK®-024 and 2000 g deionized water was added to the prepolymer over 15 mins of time and digested for the next 30 mins. A dispersion was then heated to 55 °C, and acetone was removed under vacuum to get the volume parameters.

[0110] A bluish-white, stable dispersion was obtained, exhibiting the following properties: solid content of 36.3%, pH of 7.61, and a viscosity of 350 cPs as measured by a Brookfield viscometer at 25 °C. The mean particle diameter was found to be 208 nm, as determined by zeta potential analysis. The average molecular weight of the polymer in the dispersion was approximately 99851, indicating good dispersion characteristics and appropriate molecular structure.

[0111] Infrared (IR) analysis confirmed the presence of an unsaturation peak at 1637 cm Initially, this peak was masked due to the presence of water in the dispersion; however, upon drying, the water- related interference was removed, making the peak clearly observable. The NH bond peak at 3337 cm1showed no change in intensity, while the unsaturation peak remained unchanged in the dried state. Upon complete curing of the dispersion, the unsaturation peak disappeared, confirming the occurrence of crosslinking.

[0112] To quantify the vinyl content, proton nuclear magnetic resonance f'H-NMR.) spectroscopy was employed. Resonances at 56.13 and 5 5.56 ppm were attributed to vinyl protons bonded to double- bonded carbon atoms. While these signals are typically observed as doublets of doublets, in this case, they appeared as broad peaks, likely due to the limited resolution of the 300 MHz instrument used. Despite this, the signals were adequate for quantification.

[0113] The vinyl content was calculated based on the ratio of peak areas corresponding to one vinyl proton and three protons from the isophorone diisocyanate (IPDI) unit appearing at 5 0.93 ppm. The vinyl content with respect to isophorone diisocyanate units in the polymer backbone was determined to be 12.22%. Furthermore, the dispersion exhibits a breaking load (N) of 7.1 and a % breaking elongation of 545.

[0114] Example 3: Synthesis of vinyl-terminated polyaspartic polyurea hybrid dispersion C

[0115] In a dry four-neck glass reactor, 1388.4 g PolyTHF®2000, 77 g dimethylolpropionic acid were charged and heated to 90 °C, applying a vacuum to remove the moisture level less than 0.1%. The temperature was then brought to 50°C under a nitrogen atmosphere, and 1 g of dibutyltin dilaurate was added. After 15 mins mixing, 534.4 g of isophorone diisocyanate were charged over the 15 mins time, followed by rinsing with 222 g of acetone to obtain a prepolymer mixture. The temperature of 80 °C to 85 °C was maintained.

[0116] The prepolymer mixture was then neutralized with 52.3 g of triethylamine over 30 mins digestion. The neutralized prepolymer was extended with a mixture of 253.8 g Desmophen® NH1420 and 784 g acetone. The complete extension was held for a further 60 mins. Further, 0.6 g of monomethyl ether of hydroquinone was added and allowed to mix for the next 10 mins. 118 g of 2-hydroxyethyl methacrylate was added dropwise over 30 mins and held for the next 45 mins for complete reaction.

[0117] The resultant mixture is then transferred to a dispersion vessel and mixed at 1000-1200 rpm. A mixture of 1.5 g BYK®-024 and 3500 g deionized water was added to the prepolymer over 15 mins of time and digested for the next 30 mins. A dispersion was then heated to 55 °C and acetone was removed under vacuum to get the volume parameters.

[0118] A bluish-white, stable dispersion was obtained, exhibiting the following properties: solid content of 39%, pH of 7.65, and a viscosity of 500 cPs as measured by a Brookfield viscometer at 25 °C. The mean particle diameter was determined to be 77 nm using zeta potential analysis. The average molecular weight of the polymer in the dispersion was approximately 96,486, indicating good colloidal stability and appropriate polymer characteristics.

[0119] Infrared (IR) spectroscopy confirmed the presence of an unsaturation peak at 1637 cm Initially, this peak was masked due to the presence of water in the dispersion. Upon drying, the interference from water was eliminated, allowing the peak to become clearly visible. No change was observed in the NH bond peak at 3337 cm while the unsaturation peak remained consistent in the dried state. Upon complete curing, the unsaturation peak at 1637 cm1disappeared, indicating successful crosslinking of the unsaturated sites.

[0120] Quantification of the vinyl content was carried out using proton nuclear magnetic resonance (’H- NMR) spectroscopy. Resonances at 56.13 and 55.56 ppm were attributed to vinyl protons attached to double-bonded carbon atoms. Although these peaks typically appear as doublets of doublets, they were observed as broad signals — likely due to the limited resolution of the 300 MHz instrument used. Nevertheless, the data were sufficient for analysis. The vinyl content was calculated based on the ratio of the peak areas corresponding to one vinyl proton and three methyl protons of the isophorone diisocyanate unit at 5 0.93 ppm. The vinyl content, relative to the isophorone diisocyanate units in the polymer backbone, was found to be 10.62%.

[0121] Example 4: Synthesis of vinyl-terminated polyaspartic polyurea hybrid dispersion D

[0122] In a dry four-neck glass reactor, 696 gm PolyTHF®2000, 36.1 gm dimethylolpropionic acid were charged and heated to 90°C, followed by applying a vacuum to remove the moisture level less than 0.1%. The temperature was then brought to 50°C under a nitrogen atmosphere, and 0.5 gm of dibutyltin dilaurate was added. After 15 mins of mixing, 267.9 gm of isophorone diisocyanate were charged over the 15 mins time, followed by rinsing with 60 gm of Acetone. The temperature of 80 °C to 85 °C was maintained.

[0123] The prepolymer mixture was then neutralized with 23.2 gm of triethylamine over 30 mins of digestion. The neutralized prepolymer was extended with a mixture of 145 gm Desmophen® NH1420 and 433 gm acetone. The complete extension was held for a further 60 mins. 0.3 gm of monomethyl ether of hydroquinone was added and allowed to mix for the next 10 mins. Furthermore, 97 gm of Visiomer glycerol dimethacrylate (GDMA) was added dropwise over 30 mins and held for the next 45 mins for complete reaction.

[0124] The resultant mixture is then transferred to a dispersion vessel and mixed at 1000-1200 rpm. A mixture of 1.0 gm BYK®-024 and 2030 gm deionized water was added to the polyurea polymer over 15 mins and digested for the next 30 mins. The dispersion was then heated to 55 °C and acetone was removed under vacuum to get the volume parameters.

[0125] A bluish white stable dispersion obtained having the following properties: Solid Content 39%, pH: 8.11, 500 Cps Brookfield viscosity, mean diameter of particle size of 100 nm measured by Zetapotential. The dispersion has an average molecular weight 178979. Example 5: Synthesis of vinyl-terminated polyaspartic polyurea hybrid dispersion E

[0126] In a dry four-neck glass reactor, 607.5 gm Eternacoll UH100, 37.4 g dimethylolpropionic acid were charged and heated to 90 °C, followed by applying vacuum to remove the moisture level less than 0.1%. The temperature was then brought to 50 °C under a nitrogen atmosphere, and 0.3 g of dibutyltin dilaurate was added. After 15 mins mixing, 355 g of isophorone diisocyanate were charged over the 15 minutes, followed by rinsing with 100 g of acetone. The temperature of 80 to 85 °C was maintained.

[0127] The prepolymer mixture was then neutralized with 25 gm of TEA over 30 mins digestion. The neutralized prepolymer was extended with a mixture of 167.5gm g Desmophen NH1420 and 423 g acetone. The complete extension was held for a further 60 mins. 0.3 g of MEHQ was added and allowed to mix for the next 10 mins. 170 g of HEMA was added dropwise over 30 mins and held for the next 45 mins for complete reaction.

[0128] The resultant mixture is then transferred to a dispersion vessel and mixed at 1000-1200 rpm. A mixture of 2 g BYK 024 and 1900 g deionized water was added to the prepolymer over 15 mins and digested for the next 30 mins. A dispersion was then heated to 55 °C, and acetone was removed under vacuum to get the volume parameters.

[0129] Example 6: Synthesis of pure acrylic dispersion (Comparative example)

[0130] About 425.42 g of demineralized water, ammonium hydroxide, and 1 g of sodium bicarbonate were added to raise the pH to 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® ESb 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding pre-emulsion consisting of 0.5 g of Azobis isobutyro-nitrile, 20 g of methyl methacrylate, 40 g of butyl acrylate, 1 g of Rhodapex® esb 28, and 30 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 2.2 g of Azobis isobutyronitrile, 80 g of methyl methacrylate, 140 g of butyl acrylate, 12 g of Rhodapex® esb 28, 2 g of Rhodoline® WA40, 3.5 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in the range of 72 °C to 78 °C to obtain pure acrylate dispersion. The pure acrylate dispersion was digested at 80 °C to 85 °C for Ihr.

[0131] A bluish-white stable emulsion with the following properties: Solid Content 29.7 %, pH: 6.21, 20 cps Brookfield viscosity, mean diameter of particle size of 115 nm measured by Zetapotential. The reactor hygiene was not satisfactory and had a grit of about 6 % emulsion.

[0132] The prepared sample passes the calcium ion electrostatic stability test. There was a single Tg at - 2.99 °C and an overall free monomer of 0.34 %. On applying the emulsion as a film, it was noted that the water uptake of pure acrylate film was 35.2 %.

[0133] The NMR signals demonstrate the resonances at chemical shift values, 5 4.1, 3.6, 2.5 to 1.2 ppm, corresponding to -OCH2, -OCH3, and -CH2 protons of the acrylate unit. There were no shift signals in the range 5 5 to 6.5 ppm corresponding to vinyl protons. The H1NMR analysis of the prepared sample deduces that the free vinyl concentration in % with respect to the acrylate moiety was 0%, indicating a reaction efficiency of 100 %.

[0134] Example 7: Synthesis of acryl-polyaspartic polyurea hybrid emulsion A

[0135] About 368 g of deionized water was added to dilute the 85 g of vinyl-terminated polyaspartic polyurea hybrid dispersion A, synthesized as per the procedure described in Example 1. Ammonium hydroxide was added to raise the pH to 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® Esb 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding pre-emulsion consisting of 0.5 g of Azobis isobutyronitrile, 20 g of methyl methacrylate, 40 g of butyl acrylate, 1 g of Rhodapex® esb 28, and 30 g of de-mineralized water was added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 2.5 g of azobis isobutyronitrile, 70 g of methyl methacrylate, 122 g of butyl acrylate, 12 g of Rhodapex® ESB 28, 2 g of Rhodoline® WA40, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in the range of 72 to 78 °C to obtain a acryl-polyaspartic polyurea hybrid emulsion. The acryl-polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0136] The resulting product was a uniform acryl-polyaspartic polyurea hybrid emulsion with 136 g agglomerates after filtration with the following properties: Solid Content 27.7%, pH: 7.5, 25 cps Brookfield viscosity, mean diameter of particle size of 128 nm measured by Zetapotential. The emulsion has an average molecular wt. 707087.

[0137] Further, the prepared emulsion failed the calcium ion electrostatic stability test. A single Tg at -5 °C and an overall free monomer of 0.94 % was noted. On applying the emulsion as film, it was noted that the water uptake of the film was 18.9 % in comparison to pure acrylate's 35.2 % and pure polyurethane dispersion 27.7 %.

[0138] Example 8: Synthesis of acryl-polyaspartic polyurea hybrid emulsion B

[0139] About 368 g of deionized water was added to dilute the 85 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesized as per the procedure described in Example 1. Ammonium hydroxide and 1 g of sodium bicarbonate were added to raise the pH to 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® ESB 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding preemulsion consisting of 0.5 g of Azobis isobutyronitrile, 20 g of methyl methacrylate, 40 g of butyl acrylate, 1 g of Rhodapex® ESB 28, and 30 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 2.5 g of azobis isobutyronitrile, 70 g of methyl methacrylate, 122 g of butyl acrylate, 12 g of Rhodapex® ESB 28, 2 g of Rhodoline® WA40, 3.5 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in a range of 72 to 78 °C to obtain acryl-polyaspartic polyurea hybrid emulsion. The acryl-polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0140] A milky-white, stable acryl-polyaspartic polyurea hybrid emulsion was obtained with the following properties: solid content of 30.7%, pH of 7.2, and a Brookfield viscosity of 20 cPs measured at 25 °C. The mean particle diameter was determined to be 108 nm using zeta potential analysis. The average molecular weight of the polymer in the emulsion was approximately 406069, indicating a high molecular weight polymer with good colloidal stability.

[0141] The prepared emulsion successfully passed the calcium ion electrostatic stability test, confirming its resistance to destabilization in the presence of multivalent cations. Differential scanning calorimetry (DSC) analysis revealed a single glass transition temperature (Tg) at -1.29 °C, suggesting the formation of a homogeneous polymer phase. The total residual free monomer content was 0.24%.

[0142] On applying the emulsion as a film, it was noted that water uptake testing showed significantly reduced water absorption for the prepared film at 12.6%, compared to 35.2% for a pure acrylate film and 27.7% for a pure polyurethane dispersion, indicating improved hydrophobicity and water resistance.

[0143] 'H-NMR. analysis was conducted to characterize the chemical structure and quantify residual unsaturation. The overlaid NMR spectra included signals from Example 2 and Example 7. Resonances observed at 5 4.1, 3.6, and in the range of 5 2.5 to 1.2 ppm correspond to -OCH2-, - OCH3, and -CEE- protons of the acrylate unit. Signals in the 5 5.0 to 6.5 ppm range were attributed to vinyl protons. Based on the integration of these signals, the free vinyl concentration relative to the acrylate moiety was calculated to be 6.88%, indicating a high reaction efficiency of 93.12%. Furthermore, the dispersion exhibits a breaking load (N) of 3 and a % breaking elongation of 58.6. Example 9: Synthesis of acryl-polyaspartic polyurea hybrid emulsion C

[0144] About 368 g of deionized water was added to dilute the 85 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesized as per the procedure described in Example 2. Ammonium hydroxide and 1 g of sodium bicarbonate were added to raise the pH to 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® ESb 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding preemulsion consisting of 0.5 g of Azobis isobutyronitrile, 20 g of Methyl methacrylate, 40 g of Butyl acrylate, 1 g of Rhodapex® esb 28, and 30 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 2.5 g of Azobis isobutyronitrile, 70 g of Methyl methacrylate, 122 g of Butyl acrylate, 12 g of Rhodapex® esb 28, 2 g of Rhodoline® WA40, 3.5 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in a range of 72 to 78 °C to obtain acryl-polyaspartic polyurea hybrid emulsion. The acryl-polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0145] A milky-white, stable acryl-polyaspartic polyurea hybrid emulsion was obtained with the following properties: solid content of 28.7%, pH of 7.8, and a Brookfield viscosity of 20 cPs measured at 25 °C. The mean particle diameter was determined to be 151 nm via zeta potential measurements. The average molecular weight of the polymer in the emulsion was approximately 238,339, indicating successful formation of a stable high-molecular-weight polymeric system.

[0146] The prepared emulsion demonstrated excellent stability, passing the calcium ion electrostatic stability test. Differential scanning calorimetry (DSC) analysis revealed a single glass transition temperature (Tg) at -3.97 °C, confirming the presence of a uniform polymer phase. The total residual free monomer content was low, measured at 0.17%.

[0147] On applying the emulsion as a film, it was noted that water uptake testing of the dried film showed a significant reduction in water absorption, with a value of 11.0%, compared to 35.2% for a pure acrylate film and 24.8% for a pure polyurethane dispersion (PUD) film, indicating enhanced hydrophobicity and reduced permeability.

[0148] 'H-NMR spectral analysis was used to evaluate the chemical composition and monitor residual vinyl functionality. Characteristic resonances in NMR signals were observed at 54.1, 3.6, and 2.5- 1.2 ppm, corresponding to -OCH2-, -OCH3, and -CEL>- protons of the acrylate units. Notably, no resonances were detected in the 5 5.0 to 6.5 ppm range, which corresponds to vinyl protons, indicating the absence of residual vinyl groups. The free vinyl content relative to the acrylate moiety was calculated to be 0%, confirming a reaction efficiency of 100%. Furthermore, the dispersion exhibits a breaking load (N) of 2.78 and a % breaking elongation of 70.7. Example 10: Synthesis of acryl-polyaspartic polyurea hybrid emulsion D

[0149] About 241 g of demineralized water was added to dilute the 360 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesized as per the procedure described in Example 2. Ammonium hydroxide and 1 g of sodium bicarbonate were added to raise the pH to 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® ESb 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding preemulsion consisting of 0.5 g of Azobis isobutyronitrile, 15 g of methyl methacrylate, 30 g of butyl acrylate, 1 g of Rhodapex® esb 28, and 30 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 1.6 g of Azobis isobutyronitrile, 55 g of Methyl methacrylate, 80 g of Butyl acrylate, 12 g of Rhodapex® esb 28, 2 g of Rhodoline® WA40, 3 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in a range of 72 to 78 °C to obtain acryl-polyaspartic polyurea hybrid emulsion . The acryl- polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0150] A milky white stable acryl-polyaspartic polyurea hybrid emulsion with the following properties: Solid Content 33.12 %, pH: 7.5, 20 cps Brookfield viscosity, mean diameter of particle size of 171 nm measured by Zetapotential. The emulsion has an average molecular wt. 267711.

[0151] The prepared sample passes the calcium ion electrostatic stability test. There was a single Tg at - 3.04 °C and an overall free monomer of 0.2 %. On applying the emulsion as a film, it was noted that the water uptake of the film was 11.8 % in comparison to pure acrylate's 35.2 % and pure polyurethane dispersion 24.8 %.

[0152] The NMR signals of example 3 and example 9 demonstrate NMR signal overlay. The resonances at chemical shift values, 54.1, 3.6, 2.5 to 1.2 ppm correspond to -OCH2, -OCH3, and -CH2 protons of the acrylate unit. The shift signals in range 5 5 to 6.5 ppm correspond to vinyl protons. The H1NMR analysis of the prepared sample deduces the free vinyl concentration in % with respect to the acrylate moiety was 14.69 %, indicating a reaction efficiency of 85.31 %. Furthermore, the dispersion exhibits a breaking load (N) of 2.09 and a % breaking elongation of 220.8.

[0153] Example 11: Synthesis of acryl-polyaspartic polyurea hybrid emulsion E

[0154] About 234 g of deionized water was added to dilute the 365 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesised as per the procedure described in Example 1. Ammonium hydroxide and 1 g of sodium bicarbonate were added to raise the pH to 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® ESb 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C.

[0155] A seeding pre-emulsion consisting of 0.5 g of Azobis isobutyronitrile, 15 g of Methyl methacrylate, 30 g of Butyl acrylate, 1 g of Rhodapex® esb 28, and 30 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 1.6 g of Azobis isobutyronitrile, 55 g of Methyl methacrylate, 80 g of Butyl acrylate, 12 g of Rhodapex® esb 28, 2 g of Rhodoline® WA40, 3 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in a range of 72 to 78 °C to obtain acryl-polyaspartic polyurea hybrid emulsion. The acryl-polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0156] A milky white stable acryl-polyaspartic polyurea hybrid emulsion with the following properties: Solid content 32.5%, pH: 6.8, 20 cPs Brookfield viscosity, mean diameter of particle size of 79 nm measured by zeta potential. The emulsion has an average molecular weight of 109,815.

[0157] The prepared sample passes the calcium ion electrostatic stability test. There was a single Tg at - 2.9 °C and an overall free monomer of 0.34%. On applying the emulsion as a film, it was noted that the water uptake of the film was 33.5% in comparison to pure acrylate (35.2%) and pure polyurethane dispersion (27.7%).

[0158] As per NMR study, the resonances at chemical shift values 5 4.1, 3.6, and 2.5 to 1.2 ppm correspond to -OCH2, -OCH3, and -CH2 protons of the acrylate unit was obtained. The shift signals in the range 5 5 to 6.5 ppm correspond to vinyl protons. The 'H-NMR analysis of the prepared sample deduces the free vinyl concentration in % with respect to the acrylate moiety was 8.41%, indicating a reaction efficiency of 91.6%. Furthermore, the dispersion exhibits a breaking load (N) of 5.1 and a % breaking elongation of 180.4.

[0159] Example 12: Synthesis of acryl-polyaspartic polyurea hybrid emulsion F

[0160] About 356 g of deionized water was added to dilute the 183 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesized as per the procedure described in Example 1. Ammonium hydroxide and 1 g of sodium bicarbonate were added to raise the pH to 8 - 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® esb 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C.

[0161] A seeding pre-emulsion consisting of 0.5 g of Azobis isobutyronitrile, 15 g of methyl methacrylate, 30 g of butyl acrylate, 1 g of Rhodapex® esb 28 and 30 g of di-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre- emulsion consisting of 1.6 g of Azobis isobutyronitrile, 80 g of methyl methacrylate, 115 g of butyl acrylate, 12 g of Rhodapex® esb 28, 2 g of Rhodoline® WA40, 3 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in a range of 72 to 78 °C to obtain acryl-polyaspartic polyurea hybrid emulsion. The acryl-polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0162] A milky white stable emulsion with the following properties: Solid content 31.6%, pH: 7.0, 20 cPs Brookfield viscosity, mean diameter of particle size of 93 nm measured by zeta potential. The emulsion has an average molecular weight of 204,887. The prepared sample passes the calcium ion electrostatic stability test. There was a single Tg at -0.7 °C and an overall free monomer content of 0.15%. Furthermore, the dispersion exhibits a breaking load (N) of 3.7 and a % breaking elongation of 99.2.

[0163] Example 13: Synthesis of acryl-polyaspartic polyurea hybrid emulsion G

[0164] About 360 g of de-mineralized water was added to dilute the 180 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesised as per the procedure described in example 2. Ammonium hydroxide and 1 g of sodium bicarbonate were added to raise the pH to 8 - 9.5. 2 g of Rhodoline® WA40 and 2 g of Rhodapex® ESb 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding preemulsion consisting of 0.5 g of Azobis isobutyronitrile, 15 g of Methyl methacrylate, 30 g of Butyl acrylate, 1 g of Rhodapex® esb 28, and 30 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 1.6 g of Azobis isobutyronitrile, 80 g of Methyl methacrylate, 115 g of Butyl acrylate, 12 g of Rhodapex® esb 28, 2 g of Rhodoline® WA40, 3 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 2 hr, keeping the temperature in the range of 72 to 78 °C to obtain an acryl-polyaspartic polyurea hybrid emulsion. The acryl- polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0165] A milky white stable emulsion with the following properties: Solid Content 28.8 %, pH: 7.3, 20 cps Brookfield viscosity, mean diameter of particle size of 156 nm measured by Zetapotential. The emulsion has an average molecular weight. 200275. The prepared sample passes the calcium ion electrostatic stability test. There was a single Tg at -0.7 °C and an overall free monomer of 0.15 %. Furthermore, the dispersion exhibits a breaking load (N) of 3.26 and a % breaking elongation of 125.4.

[0166] Example 14: Synthesis of acryl-polyaspartic polyurea hybrid emulsion H

[0167] About 137 g of de-mineralized water was added to dilute the 142 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesized as per the procedure described in Example 3. Ammonium hydroxide and 1 g of sodium bicarbonate were added to raise the pH to 9.5. 1.5 g of Rhodoline® WA40 and 3.5 g of Rhodapex® ESB 28 were added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding preemulsion consisting of 0.9 g of Azobis isobutyronitrile, 33 g of methyl methacrylate, 67 g of butyl acrylate, 2 g of Rhodapex® esb 28, and 15 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre-emulsion consisting of 3.7 g of Azobis isobutyronitrile, 115 g of methyl methacrylate, 205 g of butyl acrylate, 20 g of Rhodapex® esb 28, 3.5 g of Rhodoline® WA40, 5.5 g of methacrylic acid, 1 g of sodium bicarbonate, and 150 g of de-mineralized water was started and continued for 4 hr, keeping the temperature in the range of 72 to 78 °C to obtain an acryl-polyaspartic polyurea hybrid emulsion. The acryl-polyaspartic polyurea hybrid emulsion was digested at 80 to 85 °C for Ihr.

[0168] A milky white stable emulsion with the following properties: Solid Content 49.1 %, pH: 8.4, 20 cps Brookfield viscosity, mean diameter of particle size of 128 nm measured by Zetapotential. The emulsion has an average molecular weight of 445069.

[0169] The prepared sample passes the calcium ion electrostatic stability test has an overall free monomer of 0.10 %. Furthermore, the dispersion exhibits a breaking load (N) of 3.12 and a % breaking elongation of 83.1.

[0170] Example 15: Synthesis of acryl-polyaspartic polyurea hybrid emulsion I

[0171] About 200 g of de-mineralized water, Ammonium hydroxide, and 1 g of sodium bicarbonate were added to raise the pH to 9.5. 3.5 g of Rhodapex® ESB 28 was added to generate the micelle in the system under continuous stirring. The temperature of the reaction mixture was raised to 75 °C. A seeding pre-emulsion consisting of 0.9 g of Azobis isobutyronitrile, 10 g of Methyl methacrylate, 25 g of Butyl acrylate, 1.5 g of Rhodapex® esb 28, and 25 g of de-mineralized water was prepared and added to the reaction mixture to have in-situ seed formation. After 15 min, a feed of pre- emulsion consisting of 2.5 g of Azobis isobutyronitrile, 115 g of Methyl methacrylate, 200 g of Butyl acrylate, 15 g of Rhodapex® esb 28, 3 g of Rhodoline® WA40, 3 g of methacrylic acid, 1 g of sodium bicarbonate, and 80 g of de-mineralized water was started and continued for 2.5 hr, keeping the temperature in a range of 72 to 78 °C. After the completion of the monomer feed rate, a mixture of 5 g of vinyl-terminated PU synthesized as per example 5 and 50 g of de-mineralized water was added continuously in 30 min to obtain a polyaspartic polymer. Further, the reaction mixture was digested at 80 to 85 °C for Ihr.

[0172] A bluish-white stable emulsion with the following properties: Solid Content 34.8 %, pH: 7.8, 20 cps Brookfield viscosity, mean diameter of particle size of 163 nm measured by Zetapotential. The reactor hygiene was dissatisfactory with grit of 14 %, and the emulsion had an average molecular wt. 329753.

[0173] The prepared sample passes the calcium ion electrostatic stability test, having an overall free monomer of 0.23 %.

[0174] Example 16: Synthesis of acryl-polyaspartic polyurea hybrid emulsion J

[0175] The experiment was performed in a similar manner to that of Example 15. With only difference of the mixture of 5 g of vinyl-terminated polyaspartic polyurea hybrid dispersion, synthesized as per example 4, and 50 g of Di-mineralized water was added to the polyaspartic polyurea polymer simultaneously along with the monomer feed instead of after the completion of the monomer feed.

[0176] A bluish-white stable emulsion with the following properties: Solid Content 35.2 %, pH: 7.8, 20 cps Brookfield viscosity, mean diameter of particle size of 153 nm measured by Zetapotential. The reactor hygiene was satisfactory with a grit of 1.5 %, and the emulsion had an average molecular weight of 328083. An overall comprehensive data for Example 6- Example 16 is provided in Table 1.

[0177] Further, two experiments were conducted using polyaspartic polyurea polymer (synthesized as provided in example 2) (15 wt%). In the first experiment, polyurethane dispersion was incorporated into the reactor charge, while in the second, it was introduced separately alongside the monomer addition. Both batches were processed smoothly, with no observable differences in the reactor's performance, whether polyurethane dispersion was added directly or in parallel with the monomer.

[0178] Example 17: Synthesis of colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion A In a five-neck glass kettle, 1.95 g polyvinyl alcohol (8 / 88), 1.35 g polyvinyl alcohol (BP17A), and 29.815 g demineralized water were taken. The kettle was heated and charged up to 90°C for 1.5 hours. Then it was cooled to 80°C, and 15.0 g vinyl-terminated polyaspartic polyurea hybrid dispersion (synthesized as provided in example 1) was added with 1.0 g demineralized water. 0.024 g Foamasters® with 0.16 g DM water, 0.027 g Di-ammonium phosphate, 0.009 g Ammonium per sulphate (APS), 0.002 g Sodium Bi sulphite & 0.6 g demineralized water. Further, 3.0 g seed (Vinyl Acetate Monomer) was added at 75°C - 6°C slowly in 30-50 minutes and waited for exotherm in 20- 30 minutes. 0.002 g Sodium Bisulfite was added with 0.1 g demineralized water, before adding 43.5 g Vinyl Acetate Monomer (VAM) & 0.012 g Ammonium per sulphate with 1.5 g demineralized water were added in 4 hours at 80±2°C. After 30 minutes, 0.001 g ammonium persulfate was added along with 0.10 g demineralized water. The mixture was digested for 60 minutes, then cooled to 70°C, followed by the addition of 0.025 g Tertiary Butylhydroperoxide (TBHP) & 0.015 g sodium formaldehyde sulphoxylate (SFS) with 0.28 g demineralized water. The conditions were maintained for 15 minutes, and then at room temperature, 0.067g Foamaster was added along with 0.20gm demineralized water. Then add 0.135 g Biocide Proxcel GXL with 0.20gm demineralized water & water dilution was carried out.

[0179] Example 18: Synthesis of colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion B

[0180] In a five-neck glass reaction kettle, 1.95 g of polyvinyl alcohol (PVA 8 / 88), 1.35 g of polyvinyl alcohol (PVA BP17A), and 29.315 g of deionized (DM) water were charged. The mixture had been heated to 90°C and maintained at that temperature for 1.5 hours with continuous stirring to ensure complete dissolution of the polymers. Afterward, the reaction mixture was allowed to cool to 80°C. At this point, 0.024 g of Foamaster, 0.027 g of di-ammonium phosphate, 0.009 g of ammonium persulfate (APS), 0.002 g of sodium bisulfite, and 0.76 g of demineralized water were added to the system.

[0181] Once the temperature was dropped to 75-76°C, a seed feed of 3.0 g vinyl acetate monomer (VAM) was added slowly over a period of 30-50 minutes. The reaction was monitored for the onset of an exothermic reaction, which typically occurred within 20-30 minutes. Prior to initiating the vinyl acetate monomer addition, 0.002 g of sodium bisulfite in 0.10 g of demineralized water had been added.

[0182] The main monomer feed consisted of 42.5 g of vinyl acetate monomer, 15.0 g of vinyl-terminated polyaspartic polyurea hybrid dispersion (synthesized as provided in example 1) and 2.5 g of demineralized water, alongside 0.012 g of ammonium persulfate dissolved in 1.5 g of demineralized water. This mixture was fed into the reactor over a period of 4 hours while maintaining the temperature at 80 ± 2°C. After 30 minutes from the end of this addition, a further 0.001 g of ammonium persulfate in 0.10 g of demineralized water had been introduced.

[0183] Following the monomer addition, the mixture was subjected to a digestion period of 60 minutes. The temperature had then been reduced to 70°C, at which point 0.025 g of tertiary butyl hydroperoxide (TBHP), 0.015 g of sodium formaldehyde sulfoxylate (SFS), and 0.28 g of demineralized water had been added. The mixture had been held for 15 minutes to complete the redox reaction.

[0184] Finally, after cooling to room temperature, 0.067 g of Foamaster S in 0.20 g of demineralized water had been added, followed by the addition of 0.135 g of biocide (PROXEL™ GX) in 0.20 g of demineralized water and 0.926 g of dilution water to complete the formulation.

[0185] It had been observed that the simultaneous addition of vinyl-terminated polyaspartic polyurea hybrid dispersion (synthesized as provided in example 1) with vinyl acetate monomer, or the preaddition of polyaspartic polyurea polymer (synthesized as provided in example 2) into the polyvinyl alcohol solution during the initial charge, had resulted in good reactivity. However, the final product showed poor water resistance under these conditions.

[0186] Infrared analysis shows that the unsaturation peak at 1642 cm ' present in SDD 109 is absent in both final polymers with acrylic and acrylate functionality. This indicates that unbonded or unreacted acrylic polyurethane dispersion is not present, suggesting that the reaction likely went to completion.

[0187] Thus, it can be interpreted that

[0188] • The absorption peak of allyl groups (C=C) at 1642 cm ', attributed to the vinyl polyurethane dispersion, is not observed in PUV-2, PUV-3, or SR-2.

[0189] • From the 'H NMR spectrum, resonances at 5 6.13 and 5.56 ppm are assigned to protons attached to vinyl (H-C=C-H) double bond carbons. The absence of these resonances in PUV-2 and PUV-3 indicates that an addition reaction has occurred on the vinyl bond.

[0190] • The resonances at 5 4.8, 1.9, and 1.7 ppm correspond to -CH, -CH?, and -CFL> protons of the vinyl acetate unit. A weak signal at 5 0.93 ppm is attributed to methyl protons from the isophorone diisocyanate units.

[0191] • Strong peaks corresponding to -CH2 and -OCH2 protons from the polyol backbone in polyurethane dispersion likely overlap with peaks from the DMSO-de solvent. Due to the low concentration of polyurethane dispersion, base peaks from the PU backbone are fully resolved.

[0192] • Further analysis, such as subtracting the spectrum of the neat solvent, could provide a more detailed understanding of the final hybrid sample.

[0193] It was noted that the simultaneous addition of vinyl -terminated poly aspartic polyurea hybrid dispersion (synthesized as provided in example 1) with vinyl acetate monomer or the use of polyaspartic polyurea polymer (synthesized as provided in example 2) in the reactor charge with polyvinyl alcohol solution showed good reactivity. However, the water resistance of the dispersion was noted to be poor.

[0194] Example 19: Synthesis of colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion C In a five-neck glass kettle, 1.95 g of polyvinyl alcohol (8 / 88), 1.35 g of polyvinyl alcohol (BP17A), and 37.882 g of deionized water were charged and heated to 90°C for 1.5 hours. The mixture was then cooled to 80°C, and 0.024 g of Foamasters® was added along with 0.16 g of deionized water, followed by 0.027 g of diammonium phosphate, 0.009 g of ammonium persulfate (APS), 0.002 g of sodium bisulfite, and 0.6 g of deionized water. Seed vinyl acetate monomer (VAM) of 4.9 g was added slowly over 30-50 minutes at 75-76°C, and the mixture was allowed to exotherm over 20-30 minutes. Before starting the main vinyl acetate monomer addition, 0.002 g of sodium bisulfite with 0.1 g of deionized water was added. Then, 46.1 g of vinyl acetate monomer, 0.979 g of N-methylol acrylamide (NMA 50%) with 2.94 g of deionized water, and 0.012 g of ammonium persulfate with 1.5 g of deionized water were added gradually over 4 hours at 80 ± 2°C. After 30 minutes, 0.001 g of ammonium persulfate with 0.10 g of deionized water was added, followed by a digestion period of 60 minutes. The mixture was cooled to 70°C, then 0.025 g of tertiary butyl hydroperoxide (TBHP) and 0.015 g of sodium formaldehyde sulfoxylate (SFS) with 0.28 g of deionized water were added and held for 15 minutes. At room temperature, 0.067 g of Foamasters® with 0.20 g of deionized water was added, followed by 0.135 g of biocide Proxcel GXL with 0.20 g of deionized water and 0.50 g of dilution water.

[0195] Example 20: Synthesis of colloid stabilized polyvinyl acetate-polyurea hybrid dispersion D In a five-neck glass kettle, 1.95 g of polyvinyl alcohol (8 / 88), 1.35 g of polyvinyl alcohol (BP17A), and 33.641 g of deionized water were charged and heated to 90°C for 1.5 hours. The mixture was then cooled to 80°C, and 10.0 g of vinyl-terminated polyaspartic polyurea hybrid dispersion (synthesized as provided in example 3) with 2.0 g of deionized water was added. Following this, 0.024 g of Foamasters® with 0.16 g of deionized water, 0.027 g of diammonium phosphate, 0.009 g of ammonium persulfate (APS), 0.002 g of sodium bisulfite, and 0.6 g of deionized water were added. Seed vinyl acetate monomer (VAM) of 4.9 g was slowly added over 30-50 minutes at 75- 76°C, and the mixture was allowed to exotherm over 20-30 minutes. Before the main addition of vinyl acetate monomer, 0.002 g of sodium bisulfite with 0.1 g of deionized water was added. Then, 42.2 g of vinyl acetate monomer and 0.012 g of ammonium persulfate with 1.5 g of deionized water were added gradually over 4 hours at 80 ± 2°C. After 30 minutes, 0.001 g of ammonium persulfate with 0.10 g of deionized water was added, followed by a digestion period of 60 minutes. The mixture was cooled to 70°C, then 0.025 g of tertiary butyl hydroperoxide (TBHP) and 0.015 g of sodium formaldehyde sulfoxylate (SFS) with 0.28 g of deionized water were added and held for 15 minutes. At room temperature, 0.067 g of Foamasters® with 0.20 g of deionized water was added, followed by 0.135 g of biocide Proxcel GXL with 0.20 g of deionized water and 0.50 g of dilution water.

[0196] A comprehensive overview of the physico-mechanical properties of Examples 19 and 20 are provided in Table 3.

[0197] Table 3

[0198] It can be noted that the incorporation of polyurethane dispersion improves the tensile strength.

[0199] Example 21: Synthesis of colloid stabilized polyvinyl acetate-polyurea hybrid dispersion E

[0200] In a five-neck glass kettle, 1.95 g of polyvinyl alcohol (8 / 88), 1.35 g of polyvinyl alcohol, and 32.391 g of deionized water were charged and heated to 90°C for 1.5 hours. The mixture was then cooled to 80°C, and 9.5 g of vinyl-terminated polyaspartic polyurea hybrid dispersion (synthesized as provided in example 3) with 1.0 g of deionized water was added. Following this, 0.024 g of Foamasters® with 0.16 g of deionized water, 0.027 g of diammonium phosphate, 0.009 g of ammonium persulfate (APS), 0.002 g of sodium bisulfite, and 0.6 g of deionized water were added. Seed vinyl acetate monomer (VAM) of 4.9 g was slowly added over 30-50 minutes at 75-76°C, then the mixture was allowed to exotherm for 20-30 minutes. Before starting the main vinyl acetate monomer addition, 0.002 g of sodium bisulfite with 0.1 g of deionized water was added. Then, 42.2 g of vinyl acetate monomer, 0.25 g of N-methylol acrylamide (NMA 50%) with 1.5 g of deionized water, and 0.012 g of ammonium persulfate with 1.5 g of deionized water were added gradually over 4 hours at 80 ± 2°C. After 30 minutes, 0.001 g of ammonium persulfate with 0.10 g of deionized water was added, followed by a digestion period of 60 minutes. The mixture was cooled to 70°C, then 0.025 g of tertiary butyl hydroperoxide (TBHP) and 0.015 g of sodium formaldehyde sulfoxylate (SFS) with 0.28 g of deionized water were added and held for 15 minutes. At room temperature, 0.067 g of Foamasters® with 0.20 g of deionized water was added, followed by 0.135 g of biocide Proxcel GXL with 0.20 g of deionized water and 0.50 g of dilution water. Very good water resistance was observed with the addition of the crosslinker in the colloid stabilized polyvinyl acetate-polyurea hybrid dispersion. The properties achieved by implementing the dispersion on the regulated surface area are listed below,

[0201] • Enhanced water, stain, and chemical resistance;

[0202] • Attainment of non-yellowing and opaque coating;

[0203] • High performance, gloss, and anticorrosive properties;

[0204] • Excellent wood adhesive properties;

[0205] • Excellent tear strength and grab property;

[0206] • Averts yellowing on coating and provides clear as well as glossy films at high film thickness.

[0207] Moreover, the developed polyaspartic polyurea hybrid dispersion has showcased the following applications, which include but are not limited to,

[0208] • High performance and stain-resistant clear as well as opaque coating on interior and exterior paints;

[0209] • High abrasion resistance for adhering carpet, carpet padding, ceramic tiles, resilient tiles, resilient sheet goods, wooden planks and boards, wooden tiles, synthetic flooring material;

[0210] • Construction, curtain wall construction, high pressure lamination, film and foil lamination, tapes, do-it-yourself products, hobbies and crafts, manufacturing, boat construction, mobile home construction, vehicle assembly, wall covering installation, edge banding, furniture construction, countertop construction

[0211] • Elastomeric waterproofing application;

[0212] • Architectural coating, glue, adhesive, wood, enamel as well as glass coatings;

[0213] • Antimicrobial and antibacterial clear coat for home and medical applications such as glass, wall, wood, and metal substrate as mild steel (MS), tin, stainless steel (SS), aluminum, etc.

[0214] • Wood adhesive and sealant;

[0215] • Packaging coating on winery, soft drink labels, and

[0216] • Clear coat application on automobiles.

[0217] The embodiments, examples and alternatives of the preceding paragraphs or the description, including any of their various aspects or respective individual features, may be taken independently or in any combination. Features described in connection with one embodiment are applicable to all embodiments, unless such features are incompatible.

Claims

WE CLAIM:

1. A vinyl-terminated polyaspartic polyurea hybrid dispersion, comprising a vinyl- terminated polyurea polymer dispersed therein, wherein the vinyl -terminated polyurea polymer is a reaction product of i) at least one polyol moiety, ii) at least one isocyanate component, iii) at least one polyaspartic component, iv) at least one emulsifier, and v) a hydroxyl vinyl-based monomer.

2. The dispersion as claimed in claim 1, wherein the at least one polyol moiety is selected from a group consisting of polyethylene glycol, polypropylene glycol, poly isobutylene glycol, polytetrahydrofuran diol, polycarbonate diol, polycaprolactone triol, polyethylene adipate diol, poly-1, 4-butanediol adipate diol, and poly-hexanediol adipate diol.

3. The dispersion as claimed in claim 1, wherein the at least one isocyanate component is selected from a group consisting of hexamethylene- 1,6 diisocyanate, 2,2,4- trimethylhexamethylene diisocyanate, 4,4'-dicychohexylemethane diisocyanate, 2,2- diphenylmethane diisocyanate, 4,4 diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, triphenyl methane-4,4',4"-triisocyanate, naphthylene 1,5 -diisocyanate, polyphenyl polymethylene polyisocyanate, 1,2- xylylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethylxylyene diisocyanate (TMXDI), tetramethylene 1,4-diisocyanate, pentamethylene 1,5- diisocyanate, hexamethylene 1,6-diisocyanate, decamethylene diisocyanate, 1,12- dodecane diisocyanate, 2-methyl-l,5-pentamethylene diisocyanate, cyclobutane- 1, 3- diisocyanate, 1,2-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- cyclohexane diisocyanate, 2, 4-methylcyclohexane diisocyanate, 2,6-methylcyclohexane diisocyanate, 4,4'-dicyclohexyldiisocyanate, 2,4'-dicyclohexyldiisocyanate, bis(isocyanatomethyl)-cyclohexane diisocyanate, isophorone diisocyanate or a mixture thereof.

4. The dispersion as claimed in claim 1 has a NCO / OH ratio in a range of 1.2 to 2.0.

5. The dispersion as claimed in claim 1, wherein the at least one polyaspartic component is a polyaspartic ester.

6. The dispersion as claimed in claim 1, wherein the at least one emulsifier is selected from a group consisting of dimethylol propionic acid (DMPA), dimethylol butanoic acid (DMBA), citric acid, tartaric acid, diphenolic acid, hydroxymethylpropionic acid, and trimethylolpropionic acid.

7. The dispersion as claimed in claim 1, wherein the hydroxyl vinyl-based monomer is selected from a group consisting of 2-hydroxyethyl methacrylate (HEMA), 2- hydroxypropyl methacrylate (HPMA), 4-hydroxybutyl acrylate, and polyethylene glycol (meth)acrylates, glycerol dimethacrylate (GDMA).

8. The dispersion as claimed in claim 1, wherein the vinyl-terminated polyaspartic polyurea hybrid dispersion is obtained in the presence of at least one neutralizing agent, at least one defoamer, and at least one inhibitor.

9. The dispersion as claimed in claim 8, wherein the at least one neutralizing agent is a tertiary amine comprising at least one of a triethanolamine, a triethylamine, an aminomethyl propanol, a tromethamine, diisopropyl ethylamine, tetrakis-2-hydroxypropyl ethylenediamine, dimethylethanolamine, diethylethanolamine, or ethylenediamine; and the at least one inhibitor is selected from a tolu-hydroquinone or hydroquinone.

10. The dispersion as claimed in claim 1, wherein the vinyl-terminated polyaspartic polyurea hybrid dispersion has a solid content in a range of 30 to 50%.

11. An acryl-polyaspartic polyurea hybrid emulsion comprising an acryl-modified polyurea polymer, wherein the acryl-modified polyurea polymer is a reaction product of i) at least one acrylic moiety, ii) the vinyl-terminated polyaspartic polyurea hybrid dispersion as claimed in claim 1, and iii) at least one surfactant.

12. The emulsion as claimed in claim 11, wherein the at least one acrylic moiety is selected from a group consisting of methyl methacrylate, ethyl methacrylate, diethylene glycol dimethacrylate, butyl methacrylate, and any combination thereof.

13. The emulsion as claimed in claim 11, wherein the at least one surfactant is selected from an ionic or non-ionic surfactant.

14. The emulsion as claimed in claim 11, wherein the acryl-polyaspartic polyurea hybrid emulsion comprises at least one defoamer and at least one radical initiator.

15. The emulsion as claimed in claim 14, wherein the radical initiator is selected from a group consisting of alkyl peroxides, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and azo compounds.

16. A colloid-stabilized polyvinyl acetate-polyurea hybrid dispersion, comprising a colloid- stabilized polyvinyl acetate-polyurea polymer dispersed therein, wherein the colloid-stabilized polyvinyl acetate-polyurea polymer is a reaction product of i) at least one colloid component, ii) the vinyl-terminated polyaspartic polyurea hybrid dispersion as claimed in claim 1, and iii) a vinyl acetate monomer.

17. The dispersion as claimed in claim 16, wherein the at least one colloid component is selected from a group comprising polyvinyl alcohol, alkyl hydroxy ethyl cellulose, and glycols.

18. The dispersion as claimed in claim 16, wherein the colloid-stabilized polyvinyl acetate- polyurea hybrid dispersion comprises at least one cross-linking agent, at least one defoamer, at least one radical initiator, at least one surface-active agent, and at least one anti-microbial agent.

19. The dispersion as claimed in claim 18, wherein the at least one radical initiator is selected from a group of alkyl peroxides, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide azo compound; and the at least one cross-linking agent is selected from a group of multifunctional epoxides, polyfunctional aziridines, and di-functional isocyanates.

20. A composition comprising the vinyl-terminated polyaspartic polyurea hybrid dispersion as claimed in any of claims 1 to 10.

21. The composition as claimed in claim 20, wherein the composition is selected from a coating composition, a paint, an adhesive, a sealant, and an ink.

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