WO2019142208A1

WO2019142208A1 - Ambient temperature curable non-isocyanate polyhydroxyalkylurethane moieties with aldehyde cross linker

Info

Publication number: WO2019142208A1
Application number: PCT/IN2019/050032
Authority: WO
Inventors: Shaik Allauddin; Kiran Kumar NEHETE; Subarna Shyamroy; B P Mallik
Original assignee: Asian Paints Ltd.
Priority date: 2018-01-16
Filing date: 2019-01-12
Publication date: 2019-07-25

Abstract

Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided comprising: (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400–1600 and having n≥2, 'n' being the number of hydroxyurethane repeat units in said oligomer and/or polymer, (ii) hardener comprising "m" number of aldehyde and/ or ketone functionalities, "m" being ≥1, adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that "m+n"≥4 in said reaction product. A process for preparation of said coating or curable formulations thereof is also provided involving aldehyde and/ or ketone functionality based hardening/ cross linking at room temperature for ambient curing and film forming.

Description

TITLE: Ambient temperature curable non-isocyanate polyhydroxyalkylurethane moieties with Aldehyde Cross linker

FI ELD OF THE I NVENTI ON

The present invention provides for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising: (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer and/or polymer, (ii) hardener comprising“m” number of aldehyde and / or ketone functionalities,“m” being > 1 , adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that“m+n”>4 in said reaction product. More particularly, the present invention also provides for a process for preparation of said coating or curable formulations thereof involving aldehyde and / or ketone functionality based hardening/ cross linking at room temperature for ambient curing and film forming. More particularly, a method of delivering ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is also provided preferably on a substrate wherein said coats/films attained thereof are found to have improved drying and performance properties.

BACKGROUND ART

Polyurethane is among the most used binders in many coating industries. However, the manufacture of conventional polyurethane process has their drawbacks like safety, health and environmental concerns. That is why most of the industries and academic working towards isocyanate free polyurethanes [Non-isocyanate polyurethanes (NIPU)]. NIPU networks obtained by the reaction polycyclic carbonate/ cyclic carbonate and amines (aliphatic or cyclic or poly), this form a cross-linked polymer with polyhydroxyurethane (PHU) groups is one of the most studied. A general scheme of the reaction is shown in below Scheme 1

Scheme 1

The main route is a polyaddition of 5-membered cyclic carbonate and diamines leading to the formation of linear/branched PHUs with primary or secondary alcohols, as illustrated in above schemes. Moreover, the reactive pendant hydroxyl groups enable further post-funtionalization of the PHUs with chemical and biological functionalities.

Temperatures of above 80°C are usually required to cure or film formation of non-isocyanate PHUs with pendant hydroxyl groups. This high cure temperatures deficiency of prior art PHUs prevents them from being used in various application required curing at ambient temperatures.

Reference is drawn to Nonisocyanate polyurethanes disclosed under US 7045577 / 2002A, teaching preparation of novel carbonated vegetable oils (such as carbonated soybean oil) by reacting carbon dioxide with an epoxidized vegetable oil. The carbonated vegetable oils are advantageously used therein for producing non-isocyanate polyurethane materials.

US 7989553 /2009, relates to three-dimensional epoxy-amine polymer networks modified by a hydroxyalkyl urethane, which is obtained as a result of areaction between a primary amine (one equivalent of the primary aminegroups) and a monocyclic carbonate (one equivalent of the cyclic carbonategroups) . Such hydroxyalkyl urethane modifier is not bound chemically tothe main polymer network.

US8703648, US8975420, US8951933/2009A teaches new polysiloxane-modified polyhydroxy polyurethane resin derived froma reaction between a 5-membered cyclic carbonate compound and an amine modified polysiloxane compound. US Application20150247004 /2014A relates to a method of forming non isocyanate based polyurethane includes providing a cyclic carbonate, an amine, and a cooperative catalyst system that has a Lewis acid and a Lewis base.

Literature publications on ‘Solubility in C0₂ and carbonation studies of epoxidized fatty acid diesters’: towards novel precursors for polyurethane synthesis: Green Chem.2010, 12, 2205-2213; ‘Novel green fatty acid based bis-cyclic carbonates for the synthesis of isocyanate-free poly (hydroxyurethaneamide)s,’ RSC Adv. 2014, 4, 25795-25803; ‘A facile synthesis of aminohydroxy triglycerides from new crop oils’ J. Am. Oil. Chem. Soc. 2005, 82, 207-212; ‘Synthesis and Characterization of Polyurethane Networks Derived from Soybean-Oil-Based Cyclic Carbonates and Bioderivable Diamines’, ACS Sustainable Chem. Eng., 2016, 4 (12), pp 6551-6561, all teaches green methods of hydroxypolyurethane synthesis.

Reference is further drawn to Patents US2011/0313091 A1 & EP2397506A1, US8653174- that discloses the ambient temperature curable isocyanate free composition containing polycarbamate and aldehyde cross linker and acid catalyst.

US4520167 discloses amino-aldehyde diluent cross linker for hydroxypolyurethane structures that cures at elevated temperatures.

US7820779 discloses nanostructured hybrid liquid oligomer composition comprising at least one epoxy-functional component (A); at least one cyclic carbonate component (B); and at least one amine-functional component (C), wherein at least one epoxy-functional component (A) and amine-functional component (C) contains alkoxysilane units, wherein the composition is highly curable within a temperature range of approximately 10 to 30° Cwith formation of nanostructure under the influence of atmospheric moisture and the forming of active, specific hydroxyl groups by reaction of cyclic carbonates with amine functionalities.

US8143346 and 8450413/ 2003A, fast curable NIPU and HNIPU polymeric nanocompositions are derived upon crosslinking a mixture comprising of natural or modified nano-clay with either a monomer(s)/ oligomer(s) bearing cyclocarbonate group(s) or a m ixture of the latter with an epoxy resin, with a hardener bearing am ino groups.

Reference to prior arts is also drawn to the use of aldehydes as cross- linking agents: wherein CN 102093873 discloses a fracture liquid having the advantages of good thermal stability, salt resistance, and shear resistance, and can avoid residual slag of polym er chain group consisting of synthetic polym er 0.1 - 1 , crosslinking agent 0.1 - 1 , clay stabilizer 0.2- 1 , surfactant 0.1 -0.8, oxidant 0.001 - 0.05, and H₂0 94-99% wherein the synthetic polymer is homopolym er and polym er prepared from acrylam ide monomer, vinyl monom er, and hydrophobic monom er, and its mol. wt. is 500000- 1 0000000 and the crosslinking agent is organic amphoteric metal com plex crosslinking agent and/or aldehyde crosslinking agent.

DE291 1 062 discloses adducts of glyoxal or glutaraldehyde with polyols ( D- glucose, maltose, sucrose, amylose, glycerol) useful as molding composition binders (e.g., for sand molds) , in surfactants, and crosslinking agents which give control crosslinking of other polyhydroxycom pounds. Aldehydes crosslink with cellulosic polyols at high temperature is disclosed.

GB807851 teaches heat-resistant phenolic resins prepared by form ing the polybasic inorganic acid partial ester of a polyhydroxy aromatic compound having an unsubstituted position reactive with HCHO by reaction with H₃B0₄, H₃P0₄, or POCI₃ with heating in such a m anner that a substantial proportion of the phenolic OH groups rem ains unreacted, and then curing at an elevated tem perature with an aldehyde or compound that decomposes to an aldehyde takes place.

FR1478229 discloses urethane m ethylol ethers containing free OH groups prepared by treating 8-hydroxyethyl carbamates with HCHO at pH > 7 and etherifying with an aliphatic monoalcoholic at pH < 7. The compounds are used to prepare crosslinked polyurethane resins, as paper additives to increase the tear and wet resistance, in paper glues, as textile additives, and as aging protectors and stabilizers for synthetic resins wherein 8-hydroxyethyl m ethoxymethyl carbam ate, Me0CH2NHC02CH2CH20H, which on treatment with HCHO gave m ethylene bis ( 8-hydroxyethylurethane N- methylol methyl ether) wherein the aldehyde reacts with the amido end of a beta-hydroxyethyl carbamate and the hydroxyethyl group is etherified with an alcohol.

CN 104710642 discloses a kind of surface modifier of the polyurethane film and preparation method thereof. The surface modifier of the polyurethane film is aqueous solution of fluorosilicone-containing dialdehyde wherein the surface gets modified by using a photoinitiator that strengthens the performance of the polyurethane film .

CN 104693777 teaches an anti-scratch polyurethane film and its preparation method comprising mixing the fluorosilicone-containing dialdehyde, photoinitiator and water to form uniform solution to prepare the polyurethane film surface modifier; uniformly coating the polyurethane film surface modifier on the polyurethane film surface, carrying out UV-irradiation for initiating the crosslinking curing reaction, and drying to obtain the anti-scratch polyurethane film.

As apparent from the state of the art discussed above that while aldehyde crosslinking with polyurethane films are known the same either crosslinks with phenolic -OH groups or requires either photoinitiator based conditions or high temperature conditions or requires polyurethane binders including the presence of polymerizable unstaurations such as vinyl, acrylic, acrylamide type groups to control the cross-linking and end drying properties, and therefore it is the need of the day to explore for formulations involving selective binder and an active functional cross linker/hardener, such that the formulation is curable at ambient temperature free of any need of photoinitiator, any need of polymerizable unstauration in the NIPHU binder thereby making the process simple to thereby provide for an improved cross linked system at ambient temperatures with improveddrying and performance properties.

OBJECTS OF THE PRESENT I NVENTI ON

Thus the primary object of the present invention is to provide for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof which in comprising selective binder and hardener functionalities would be room temperature curable by aldehyde and/ or ketone functionalities employed as hardener/ cross-linker adapted for ambient curing together with improved drying and performance properties.

Another object of the present invention is to provide for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof which in comprising selective binder involving selective amine content together with select number of hydroxyurethane repeat units in said oligomer/ polymer would be free of any requirement of polymerizable unsaturated groups in the binder such as vinyl, acrylic, acrylamide type groups and yet be curable at room temperature by hardener functionalities involving aldehyde and / or ketone functionalities used as a cross-linker.

Another object of the present invention is to provide for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof providing for a reaction product of a select binder and aldehyde and / or ketone functionality based hardener that would be free of phenolic -OH groups and polymerizable unsaturated groups such as vinyl, acrylic, acrylamide type groups and yet would show improved drying and performance properties.

Yet another object of the present invention is to provide for a process of manufacture of said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations that would facilitate cured coat or curable form ulationsas a reaction product of said binder and hardener in the temperature range of about -5 to 40 °C.

Still another object of the present invention is to provide for a process of manufacture of said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof which process would be free of any photoinitiator based curing conditions and yet would be performable under ambient/ room temperature conditions. SUMMARY OF THE I NVENTI ON

Thus according to the basic aspect of the present invention there is provided an ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising:

(i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having the following structures (I) below

(i)

wherein: n> 2; x= 0-4;

R₁ R2,R₃, and R₅ comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;

R₄ comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and

(ii) hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being >1, adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that“m+n”>4 in said reaction product. It is thus the selective finding of the present invention that ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof could be attained of : (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer and/or polymer, and (ii) hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being >1, surprisingly providing said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that when “m+n”>4 in said reaction product.

According to a preferred aspect of the present invention said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided wherein said “m” number of aldehyde and/or ketone functionality based hardeners comprise selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.

Preferably said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided which is either a coating comprising ambient cured reaction product of said (i) and (ii), or, is a formulation comprising ambient curable ready to apply said (i) and (ii) as components of a formulation favouring generation of said reaction product based coating.

According to another preferred aspect of the present invention there is provided said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof having said binder and / or hardener sourced total aromatic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product. Preferably said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided wherein said aromatic content is chemically connected with the HNIPU binder and is sourced from the groups selected from the group consisting of one or more aromatic polyamines, one or more aromatic epoxy resins, one or more epoxy functional polymers, one or more benzene ring containing polymers, one or more polyanhydrides, one or more anhydride functional polymers and combinations thereof.

According to a yet another preferred aspect of the present invention said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided wherein said hardener comprises“m” number of aldehydeand/ or ketone functionalities; and

said binder base comprises amines and/or imine reacted polycyclic carbonate and/or cyclic carbonate based (HNIPU) binder, said polycyclic carbonate and/or cyclic carbonate includes reaction products of at least one aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

According to yet another preferred aspect of the present invention an ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided wherein said hardener comprises aldehyde functionality based aldehyde compound such that “m” >1 including aqueous, non-aqueous, neat liquid and solvent-borne polyaldehydes comprising acetal adduct of polyaldehyde and alcohols/glycols, schiff base adduct of polyamine/polyimine and polyaldehyde having “m” number of free aldehyde functionalities per adduct molecule including alkyl, aryl or aliphatic, cyclo aliphatic radicals that may include 1-30 or higher carbon atoms, linear and/or branched moieties, one or more hetero atoms containing functionality and includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; PARALOID™ EDGE XL-195 is a 1 ,4-cyclohexanedicarboxaldehyde; 3,4- Dimethoxybenzaldehyde; croton-aldehyde, Polysaccharide aldehydes, n- butyraldehyde, benzaldehyde, aromatic aldehydes include benzaldehyde, ortho-, para- and meta-tolualdehyde, anisaldehyde and substituted benzaldehydes having one to three substituents and wherein the substituents are selected from lower alkyl, methoxy, mono- and di- alky Iasi no, amino, nitro or halogen, m- hydroxy-benzaldehyde, 1 ,4-hydroxynaphthaldehyde, 3-

Climethylaminobenzaldehyde,4-hydroxy3-methoxybenzaldehyde, I (3 formylphenyl) 3- methyl-S-pyrazolone, I (4 formylphenyl) 3 methyl-5 pyrazolone and 1 -(2-formylphenyl) 3-methyl-5-pyrazolone, o-, m-, and p-acetoacetamino benzaldehyde, 3--brom-2-hydroxybenzaldehyde, 2 hydroxy 3 nitrobenzaldehyde, 6 hydroxy-2-methylbenzaldehyde, and 2-hydroxy-5- methylbenzaldehyde, Glyoxal solution 40 wt. % in H20, Glyceraldehyde, 4-Bromothiazole-2- carboxaldehyde, 2-lmidazolecarboxaldehyde, 5-Nitro-2-furaldehyde, 5- Formyluracil, 3-Furancarboxaldehyde , 3-Thiophenecarboxaldehyde , Furfural , Pyrrole-2-carboxaldehyde , Glutaraldehyde solution 50 wt. % in H20, Tetrahydrofuran-3-carboxaldehyde solution 50 wt. % in H20, 2,3-

Thiophenedicarboxaldehyde, 2,3,4,5,6-Pentafluorobenzaldehyde, 2,3,6- Trichlorobenzaldehyde, Pyrrole-2-carboxaldehyde, 2,4- Dihydroxybenzaldehyde,4- bromo-2-cyanobenzaldehyde,3-Chloro-5-

(trif I uorom ethyl) benzaldehyde, I sop ht hal aid ehyde,Phthaldi aldehyde,

Terephthal aldehyde, 4- FI uoro- 3- methoxy benzaldehyde, p- Anisaldehyde,3- Brom 0-5- (trif I uorom ethyl) benzaldehyde, 4-Methyl-3-(trifluoromethyl) benzaldehyde, 1 ,1' -Ferrocenedicarboxaldehyde,cyclicpolyaldehydesare trans-1 ,3- cyclohexanedicarboxaldehyde; cis- 1 ,3-cyclohexanedicarboxaldehyde; trans- 1 ,4- cyclohexanedicarboxaldehyde; cis- 1 , 4-cyclohexanedicarboxaldehyde; a mixture of 1 ,3-cyclohexanedicarboxaldehydes and 1 ,4-cyclohexanedicarboxaldehydes, exo,exo- 2,5-norbomanedicarboxaldehyde; exo,exo-2,6- norbornanedicarboxaldehyde; exo,endo- 2,5-norbomanedicarboxaldehyde; exo,endo-2,6-norbornanedicarboxaldehyde; endo, endo- 2,5- norbomanedicarboxaldehyde; endo,endo-2,6-norbornanedicarboxaldehyde product (endo and exo mixture); 3-(3-formylcyclohexyl)propanal;3-(4- formylcyclohexyl)propanal;2-(3-formylcyclohexyl)propanal; 2-(4- formylcyclohexyl)propanal; cyclododecane-1 ,4,8-tricarbaldehyde, preferably includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; paraloid™ edge xl-195 (1 ,4-cyclohexanedicarboxaldehyde) ; 3,4-

Dim ethoxy benzaldehyde.

According to another preferred aspect of the present invention said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided wherein said hardener comprises at least one or more ketone functionality based ketone compound such that “m” >1 including mono-, d i - , tri- and poly-ketone compounds, said monoketones including Methyl isobutyl ketone, Dicyclohexyl ketone, Methyl 2-pyrrolyl ketone, 2-Furyl methyl ketone, Cyclohexyl phenyl ketone, 3-Flepten-2-one, Ethyl vinyl ketone, Di ( 2 - pyridyl) ketone, Po I y ( v i n y I methyl ketone), Bis(1 -methyl-2-imidazolyl) ketone, Di-2-thienyl ketone, 1 - Isoquinolinyl phenyl ketone, Diethyl ketone, Diisobutyl ketone, Ethyl methyl ketone, Isopropyl methyl ketone, Methyl propyl ketone, Benzophenone, Acetophenone, Butyrophenone, 2', 5' -Dihydroxyacetophenone, 2- Fleptanone, 2,4- Dimethyl-3-pentanone, 4-Methoxyphenylacetone, 2- Acetylpyrrole, 2- Acetylpyridine, 3-Nonanone,lsovalerophenone, 1 ,3- Diphenyl-2- propanone, 2- Am inobenzophenone, 3- Acetylindole, 2- Acetyl-5-chlorothiophene, 2-Benzoylpyridine, 2,2,2-Triphenylacetophenone, Benzylideneacetone, Dipyridin- 4-ylmethanone, HEPTADECYL 2-NAPHTHYL KETONE, Xanthone, 2'- Aminoacetophenone, 2-Chloroacetophenone, 4,4' - Dichlorobenzophenone, 9- Acetylanthracene, 4,4' - Difluorobenzophenone,Tetraphenylcyclopentadienone, 2- lsopropyl-5-methylcyclohexanone, 9(10H)-Anthracenone, Isophorone, 1- Dimethylamino-2-propanone, 3- Am ino-2-cyclohexen- 1 -one,Dicinnamalacetone, ( Diethyl ami no) acetone, 4- Am ino-9-fluorenone,Hexaketocyclohexaneoctahydrate, Acetone, 2- Acetylpyrazine, 3- Acetyl-2,4 -dim ethylpyrrole,Acetylpyrazine,Furoin, Cyclohexanone, 1 ,1'-Carbonyldiimidazole, 2' -Hydroxyacetophenone,

Methylglyoxal 1,1 -dimethyl acetal, 4-Methylbenzophenone, 1,1- Dichloro-2- propanone, Benzophenone-3,3' ,4,4' -tetracarboxylic dianhydride, 3-Hydroxy-1 ,2- dimethyl-4(1 H)-pyridone, Ethyl 2-oxo-1 -cyclooctanecarboxylate, 1-Methyl-2- pyrrolidinone,1 - Benzyl -2- pyrrol id i none, N- Methyl pyrrol idone, 4- Hydroxy- 4- methyl - 2-pentanone; 2,2,6,6-Tetramethyl-4-piperidone,Diacetone amine Triacetone amine, ACETYLACETONE IMIDE;

said Di-ketones including 1 ,3- Dibenzoylpropane ,1,2-diketone (diacetal), 1,3- diketone (acetylacetone) , 15,4-diketone (hexane-2, 5-dione), 1,2- Naphthoquinone, 2-Methyl-1 , 4- naphthoquinone, 1 ,3- Dibenzoylbenzene, 2- Acetylcyclopentanone,4-Cyclopentene-1 ,3-dione, 4,5-DICHLORO-4-

CYCLOPENTENE-1 ,3-DIONE, 1 ,3- 1 ndandione, 4-Cyclopentene- 1 ,3-dione, Hulupinic acid,Anthraquinone,Octafluoroanthraquinone,Acetylacetone,1 -(4- MORPHOLI NYLACETYL) -2- PYRROLI Dl NONE,Glutarim ide, 4-

( Bl S( ETHOXYCARBONYL) METHYL) - 1 ,2- NAPHTHOQUI NONE;

said triketone including 2-acetyl-1 -methoxy-anthraquinone, cycloheximide, actiphenol;

said polyketones including Po I y ( v i n y I methyl ketone), polyketones,

Polyvinylpyrrolidone, polyether etherketone(PEEK) .

According to yet another preferred aspect of the present invention said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided wherein said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1 ,6-hexamethylene diamine; 1 ,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine) ; 2- methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1 ,3-propanediamine, bis- (4,4’- aminocyclo hexyljmethane, tricyclodecanediamine (or 3(4), 8(9) - bis-

(aminomethyl)tricyclo [5 .2 .I . I0]decane; 2-methylpentane-1 ,5-diamine; octylamine and hexylamine; polyalkylenam ines such as diethylenetriamine, triethylenetetram ine, tetraethylenepent amine, pentaethylenehexamine, propylenediamine, dipropylenetriam ine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trim ethylhexam ethylenediam ine, N,N’-bis-(3 -am inopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediam ine, 1,3- diaminopentane, andhexamethylenediam ine; cycloaliphatic amines such as 1, 2- or 1,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino- 4-ethylcyclohexane; 1 ,4-diamino-3, 6-diethyl-cyclohexane, 1 -cyclohexyl-3, 4- diaminocyclohexane; 4,4’-diaminodicyclohexylmethane, propane, 2,2-bis-(4- aminocyclohexyl)-methane and -pro pane, 3,3’-dimethyl-4,4’- diaminodicyclohexyl-methane, 3-amino-1 -cyclohexylaminopropane, 1,3- and 1,4- bis (amininomethyl)-cyclohexane; polyoxyalkylenaminessuchas poly (oxy ethylenediam ine), poly(oxyethylenetriamine), poly(oxypropylenediam ine) , and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethyl piperazine and 1 ,4-bis-(3’-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3-aminopropyltriethoxysilane; polyethyleneglycol monoamine, 3-am inopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

Preferably said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided wherein said cyclic ether precursors to polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/polymers thereof.

More preferably said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided wherein said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerine carbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl)-ethylene carbonate, 3,4-0-isopropylidene-D-mannitol-1 ,2:5,6- dicarbonate and D-mannitol-1 ,2:5, 6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-1 ,3-dioxolan-2-one, 4-Trifluoromethyl-1 ,3-dioxolan-2-one, bisphenol A polycarbonate, Divinylbenzene Dicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate-modified bis (4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane compound, trimethylolpropanetricyclocarbonate, chlorine- contained aliphatic tricyclocarbonates, 2-oxo-1 ,3-dioxolan-4-yl) methyl N-allyl carbamate, 4-(2-oxo- 1 ,3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxymethyl)-1 ,3-dioxolan-2- one, (2-oxo-1 ,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscyclic carbonates, 4-(2-oxo- 1 ,3-dioxolan-4-yl)butyl N-dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4-glycidyloxy phenyl)phenyl phosphine oxide (BGPPO), and poly(propy I eneg ly col ) d ig ly cidy I ether, Rosin based Cylic carbonate, Cyclic bis-carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine- contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl) 1 ,3-dioxolan-2- one, and is preferably jeffsol® glycerine carbonate.

According to a preferred aspect of the present invention said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided adapted for clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

According to another aspect of the present invention there is provided a method of providing ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof said method comprising:

a) having a binder base comprising (i) ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of amine hydrogen equivalent weight in the range of 400-1600 and having the following structures (I) below

wherein: n> 2; x = 0-4;

R₁ R₂,R3, and R₅ comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;

R₄ comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; b) having a hardener comprising “m” number of aldehyde and / or ketone functionalities,“m” being > 1 ; c) mixing said binder (a) with said hardener(b) and allowing the mixture to dry at ambient temperature of -5 to 40 °C to provide for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (a) and (b) such that m+n>4 in said reaction product.

Preferably in said method said step (b) of having a hardener comprises having “m” number of aldehyde and / or ketone functionality based hardeners including selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality. According to another preferred aspect of said method said binder and/ or hardener sources total arom atic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product.

Preferably in said method said step (a) of having a binder comprising ambient tem perature curable hydroxyl urethane oligomer and/or polym er (HNI PU) binder includes reacting polycyclic carbonate and/or cyclic carbonate with am ines and/or im ines in stoichiometric equivalents in the range from 1 : 0.4 to 1 : 2.2 respectively to yield a polymer with hydroxyurethane ( PHU) groups having am ine equivalent weight in the selective range of 400- 1 600.

More preferably, said polycyclic carbonate and/or cyclic carbonate is sourced from reactions between aryl or alkyl carbonate and diol/ glycol ; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precu rsors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

According to another preferred aspect of said method said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerine carbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl) - ethylene carbonate, 3, 4-0- isopropylidene- D-m annitol- 1 ,2: 5, 6-dicarbonate and D- mannitol- 1 ,2:5, 6-dicarbonate, isosorbide based bis-cyclic carbonate, 4- Phenyl-

1 .3-dioxolan-2-one, 4-Trifluoromethyl- 1 ,3-dioxolan-2-one, bisphenol A polycarbonate, DivinylbenzeneDicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate- modified bis(4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane com pound, trimethylolpropanetricyclocarbonate, chlorine- contained aliphatic tricyclocarbonates, 2-oxo- 1 ,3-dioxolan-4-yl) methyl N-allyl carbamate, 4- (2-oxo-

1 .3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxym ethyl) - 1 ,3-dioxolan-2- one, (2-oxo-1 ,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscycliccarbonates, 4-(2-oxo-1 ,3-dioxolan-4-yl)butyl N- dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4- g lycidy loxy phenyl)phenyl phosphine oxide (BGPPO), and poly( propy leneg lycol) diglycidylether, Rosin based Cylic carbonate, Cyclic bis- carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl)1 ,3 -dioxol any one, and is preferably jeffsol® glycerine carbonate.

According to yet another preferred aspect of said method said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1 ,6-hexamethylene diamine; 1 ,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine) ; 2-methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1 ,3-propanediamine, bis-(4,4’- aminocyclo hexyl)methane, tricyclodecanediamine (or 3(4), 8(9)-bis-

(aminomethyl)tricyclo [5 .2 .I . I0]decane; 2-methylpentane-1 ,5-diamine; octylamine and hexylamine; polyalkylenam ines such as diethylenetriamine, triethylenetetram ine, tetraethylenepentam ine, pentaethylenehexamine, propylenediamine, dipropylenetriam ine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trim ethylhexam ethylenediam ine, N,N’-bis-(3 -am inopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediam ine, 1,3- diaminopentane, andhexamethylenediam ine; cycloaliphatic amines such as 1,2- or 1 ,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino- 4-ethylcyclohexane; 1 ,4-diamino-3, 6-diethyl-cyclohexane, 1 -cyclohexyl-3, 4- diaminocyclohexane; 4,4’-diaminodicyclohexylmethane, propane, 2,2-bis-(4- aminocyclohexyl)-methane and -pro pane, 3,3’-dimethyl-4,4’- diaminodicyclohexyl-methane, 3-amino-1 -cyclohexylaminopropane, 1,3- and 1,4- bis (amininomethyl)-cyclohexane; polyoxyalkylenaminessuchas poly ( oxy et hy I enedi amine), poly ( oxy et hy I enetri amine), poly(oxypropylenediam ine) , and poly (oxypropylenetriamine); heterocyclic amines such as N-am inoethylpiperazine and 1 ,4-bis-(3’-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3-aminopropyltriethoxysilane; polyethyleneglycol monoamine, 3-am inopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

Preferably, in said method said cyclic ether precursors for generation of polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/ polymers thereof.

According to yet another preferred aspect of said method said hardener comprises aldehyde functionality based aldehyde compound such that “m”>1 including aqueous, non-aqueous, neat liquid and solvent-borne polyaldehydes comprising acetal adduct of polyaldehyde and alcohols/glycols, schiff base adduct of polyamine/polyimine and polyaldehyde having “m” number of free aldehydefunctionalities per adduct moleculeincludingalkyl, aryl or aliphatic, cyclo aliphatic radicalsthat may include 1-30 or higher carbon atoms, linear and/or branched moieties, one or more hetero atoms containing functionality and includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; PARALOID™ EDGE XL-195 is a 1 ,4-cyclohexanedicarboxaldehyde; croton-aldehyde, Polysaccharide aldehydes, n-butyraldehyde, benzaldehyde, aromatic aldehydes include benzaldehyde, ortho-, para- and meta-tolualdehyde, anisaldehyde and substituted benzaldehydes having one to three substituents and wherein the substituents are selected from lower alkyl, methoxy, mono- and d i- alky I asi no, amino, nitro or halogen, m -hydroxy-benzaldehyde, 1,4- hydroxy nap hth aldehyde, 3 -Cl i methyl ami nobenzaldehyde,4- hydroxy 3- methoxybenzaldehyde, I (3 formylphenyl) 3- methyl-S-pyrazolone, I (4 formylphenyl) 3 methyl-5 pyrazolone and 1 -(2-formylphenyl) 3-methyl-5- pyrazolone, o-, m-, and p-acetoacetaminobenzaldehyde, 3--brom-2- hydroxybenzaldehyde, 2 hydroxy 3 nitrobenzaldehyde, 6 hydroxy-2- methylbenzaldehyde, and 2-hydroxy-5- methylbenzaldehyde, Glyoxal solution 40 wt. % in H20, Glyceraldehyde, 4-Bromothiazole-2-carboxaldehyde, 2- Imidazolecarboxaldehyde, 5-Nitro-2-furaldehyde, 5-Formyluracil, 3- Furancarboxaldehyde , 3-Thiophenecarboxaldehyde , Furfural , Pyrrole-2- carboxaldehyde , Glutaraldehyde solution 50 wt. % in FI20, Tetrahydrofuran-3- carboxaldehyde solution 50 wt. % in FI20, 2,3-Thiophenedicarboxaldehyde , 2,3,4,5,6-Pentafluorobenzaldehyde, 2,3,6-Trichlorobenzaldehyde, Pyrrole- 2- carboxaldehyde, 2,4-Dihydroxybenzaldehyde,4-bromo-2-cyanobenzaldehyde,3- Chloro-5-(trifluoromethyl)benzaldehyde,lsophthalaldehyde,Phthaldialdehyde, Terephthal aldehyde, 4- Fluoro-3-methoxybenzaldehyde, p- Anisaldehyde,3- Bromo-5-(trifluoromethyl)benzaldehyde, 4-Methyl-3-(trifluoromethyl) benzaldehyde, 1 ,Y -Ferrocenedicarboxaldehyde,cyclicpolyaldehydesare trans-1 ,3- cyclohexanedicarboxaldehyde; cis- 1 ,3-cyclohexanedicarboxaldehyde; trans- 1,4- cyclohexanedicarboxaldehyde;cis-1 , 4-cyclohexanedicarboxaldehyde; a mixture of 1 ,3-cyclohexanedicarboxaldehydes and 1 ,4-cyclohexanedicarboxaldehydes, exo, exo- 2,5-norbomanedicarboxaldehyde; exo,exo-2,6- norbornanedicarboxaldehyde; exo, endo- 2,5-norbomanedicarboxaldehyde; exo,endo-2,6-norbornanedicarboxaldehyde; endo, endo -2,5- norbomanedicarboxaldehyde; endo,endo-2,6-norbornanedicarboxaldehyde product (endo and exo mixture); 3-(3-formylcyclohexyl)propanal; 3-(4- formylcyclohexy propanal; 2-(3-formylcyclohexyl) propanal; 2-(4- formylcyclohexy propanal; cyclododecane-1 ,4,8-tricarbaldehyde, preferably includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; paraloid™ edge xl-195 (1 , 4-cyclohexanedicarboxaldehyde) ; 3,4-

Dim ethoxy benzaldehyde.

According to another preferred aspect of said method said hardener comprises at least one or more ketone functionality based ketone compound such that “m” >1 including mono-, d i - , tri- and poly-ketone compounds, said monoketones including Methyl isobutyl ketone, Dicyclohexyl ketone, Methyl 2-pyrrolyl ketone,

2-Furyl methyl ketone, Cyclohexyl phenyl ketone, 3-Hepten-2-one, Ethyl vinyl ketone, Di(2- py ridy I) ketone, Po I y ( v i n y I methyl ketone), Bis(1 -methyl-2- imidazolyl)ketone, Di-2-thienyl ketone, 1 - Isoquinolinyl phenyl ketone, Diethyl ketone, Diisobutyl ketone, Ethyl methyl ketone, Isopropyl methyl ketone, Methyl propyl ketone, Benzophenone, Acetophenone, Butyrophenone, 2', 5'- Dihydroxyacetophenone, 2-Heptanone, 2,4-Dimethyl-3-pentanone, 4- Methoxyphenylacetone, 2- Acetylpyrrole, 2- Acetylpyridine, 3-

Nonanone sovalerophenone, 1 ,3- Diphenyl-2-propanone, 2-Aminobenzophenone,

3- Acetylindole, 2- Acetyl-5-chlorothiophene, 2-Benzoylpyridine, 2,2,2-

Tri phenyl acetophenone, Benzylideneacetone, Dipyridin-4-ylmethanone, HEPTADECYL 2-NAPHTHYL KETONE, Xanthone, 2' - Am inoacetophenone, 2- Chloroacetophenone, 4,4'-Dichlorobenzophenone, 9- Acetylanthracene, 4,4'- Difluorobenzophenone,Tetraphenylcyclopentadienone, 2 - Isopropyl- 5- methylcyclohexanone, 9(1 OH) -Anthracenone sophorone, 1-Dim ethyl am ino-2- propanone, 3-Amino-2-cyclohexen- 1 - on e, Dici n n am al acetone,

( Di et hy lam i no) acetone, 4- Am ino-9-fluorenone,Hexaketocyclohexaneoctahydrate, Acetone, 2- Acetylpyrazine, 3- Acetyl-2,4 -dim ethylpyrrole,Acetylpyrazine,Furoin, Cyclohexanone, 1 ,1'-Carbonyldiimidazole, 2' -Hydroxyacetophenone,

Methylglyoxal 1,1 -dimethyl acetal, 4-Methylbenzophenone, 1,1- Dichloro-2- propanone, Benzophenone-3,3' ,4,4' -tetracarboxylic dianhydride, 3-Hydroxy-1 ,2- dimethyl-4(1 H)-pyridone, Ethyl 2-oxo- 1 -cyclooctanecarboxylate, 1 -Methyl-2- pyrrolidinone,1 -Benzyl-2-pyrrolidinone,N-Methylpyrrolidone,4-Hydroxy-4-methyl- 2-pentanone,2,2,6,6-Tetramethyl-4-piperidone,Diacetone am ine Tri acetone amine, ACETYLACETONE IMIDE;

said Di-ketones including 1 ,3- Dibenzoylpropane, 1,2-diketone (diacetal), 1,3- diketone (acetylacetone) , 15,4-diketone (hexane-2, 5-dione), 1,2- Naphthoquinone, 2-Methyl-1 , 4- naphthoquinone, 1 ,3- Dibenzoylbenzene, 2-

Acetylcyclopentanone,4-Cyclopentene-1 ,3-dione, 4,5-DICHLORO-4-

CYCLOPENTENE-1 ,3-DIONE, 1 ,3- 1 ndandione, 4-Cyclopentene- 1 ,3-dione, Hulupinic acid, Anthraquinone, Octafluoroanthraquinone, Acetylacetone, 1-(4- MORPHOLI NYLACETYL) -2- PYRROLI Dl NONE, Glutarimide, 4-

( Bl S( ETHOXYCARBONYL) METHYL) - 1 ,2- NAPHTHOQUI NONE;

said polyketones including Po I y ( v i n y I methyl ketone), polyketones,

Polyvinylpyrrolidone, polyether ether ketone( PEEK) .

Preferably said method of providing for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof as clear coat or pigmented coat includes one or more polymer blend, additives, fillers, extender and optionally pigments.

According to another aspect of the present invention a method of delivering ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof, said method comprising: i. Having a base binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having the following structure (I) below

wherein: n> 2; x = 0-4;

R₁.R₂.R₃, and R₅ comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;

R₄ comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moietiescontaining 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and ii. Having a hardener comprising “m” number of aldehyde and / or ketone functionalities,“m” being > 1

iii. Mixing said binder base (i) with said hardener (ii); and

iv. Applying coating of the above mixture of step (iii) above on a substrate to thereby deliver ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating upon drying at ambient temperature of -5 to 40°C based on generation of a reaction product having m+n >4 in said reaction product.

Preferably in said method of delivering ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating said hardener of step (ii) comprises said“m” number of aldehyde and/or ketone functionality based hardeners comprising selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.

More preferably in said method said substrates include Metal, Wood, Plastic, Aluminum, Glass, Paper, Gypsum, Cement, Porus bricks, Sand, and wherein said method includes either delivering the coating directly on any of these substrates or on top of a suitable primer, and also includes top-coating said coating with any other type of binder said coating provided as a topcoat or undercoat being either a clear-coat or a pigmented coat.

According to yet another preferred aspect said applying the coating includes applying by brush, spray, roller, spin coater, bar coater, applicator, poring, impregnating, dipping in resin, wounding of solid resin on said substrate.

DETAI LED DESCRI PTI ON OF THE PRESENT I NVENTI ON

As discussed hereinbefore, the present invention provides for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising: (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) as the select binder of selective amine hydrogen equivalent weight in the range of 400- 1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer/ polymer, (ii) hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being >1, adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that “m+n”>4 in said reaction product. Particularly, the present invention also provides for a process for preparation of said coating or curable formulations thereof involving aldehyde and / or ketone functionality based hardener for cross linking with said select binder at room temperature curing or film forming, which coats/ films have improved drying and performance properties.

According to an embodiment of the present invention said select polymeric/ oligomeric binder (HNIPU)s of the present invention of select amine equivalent weight in the range of 400-1600 comprises following structure(l) below

(I) wherein: n> 2; x = 0-4;

R₁ R2,R₃, and R₅ comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties; R₄ comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and Said select hardener comprises “m” number of aldehyde and / or ketone functionalities,“m” being >1 and upon mixing said binder (I) with said hardener and further allowing the mixture to dry at ambient temperature of -5 to 40 °C provides for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said binder and hardener such that m+n>4 in said reaction product.

Preferably said “m” number of aldehyde and/or ketone functionality based hardeners comprise selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.

More preferably said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is either a coating comprising ambient cured reaction product of said (i) and (ii), or, is a formulation comprising ambient curable ready to apply said (i) and (ii) as components of a formulation favouring generation of said reaction product based coating.

Advantageously, said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprise select binder functionalities of selective amine content together with select hydroxyurethane repeat units in said binder oligomer/ polymer that is further free of any requirement of polymerizable unsaturated groups in the binder such as vinyl, acrylic, acrylamide type groups to be curable at room temperature by aldehyde and / or ketone functionalities used as a hardener/cross-linker adapted for improved drying and performance properties of said coats/films in terms of gloss, hardness and scratch resistance.

According to another aspect of the present invention there is provided said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising a reaction product of selective amine content and selective hydroxyurethane repeat units based HNIPU oligomer/ polymer with aldehyde and / or ketone functionalities, which NIPHU is free of phenolic -OH groups and polymerizable unsaturated groups such as vinyl, acrylic, acrylamide type groups and yet shows improved drying and performance propertiesin terms of gloss, hardness and scratch resistance.

According to another aspect a process for providing said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided.

EXAMPLES:

A process for preparation of ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided comprising the steps of : providing HNI PUs oligomer/ polym er comprising select binder functionalities of selective am ine content together with select hydroxyurethane repeat units in said NI PHU oligom er/ polym er; further providing a hardener comprising aldehyde and / or ketone functionalities; m ixing said binder with said hardener and allowing the m ixture to dry at am bient temperature of -5 to 40 °C to provide for said ambient cured hydroxyl non-isocyanate polyurethane ( HNI PU) based coating having a reaction product of said (a) and (b) such that m+ n> 4 in said reaction product.

Advantageously, said reaction product is formed at room tem perature and free of any photoinitiators to obtain therefrom said aldehyde and / or ketone functionalities cured HNI PUs with improved drying and performance propertiesin terms of gloss, hardness and scratch resistance.

The select binder com prising ambient temperature curable hydroxyl urethane oligomer and/or polym er (HNI PU) binder of the present invention having the above structure ( I) is obtained according to an embodiment of the present invention :

by reacting polycyclic carbonate and/or cyclic carbonate with amines and/or im ines in stoichiometric equivalents in the range from 1 : 0.4 to 1 :2.2 respectively to yield a polym er with hydroxyurethane ( PHU) groups having am ine equivalent weight in the selective range of 400- 1 600.

According to an embodim ent of the present invention said polycyclic carbonate and/or cyclic carbonate is sourced from reactions between aryl or alkyl carbonate and diol/ g ly col ; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

According to an embodiment of the present invention the ambient cured hydroxyl non- isocyanate polyurethane ( HNI PU) based coating or curable form ulations thereof comprising said hydroxy-NI PUs (non-isocyanate polyurethanes, HNIPUs) binder is characterized by:

(a) selective amine hydrogen equivalent weight (AHEW) in the range of 400 to 1600, (b) Viscosity [Gardner-Holdt (Units)] in the range of: K-L to Z7-Z8, (c) One or more Amide linkages in the binder polymer molecule and optionally, comprises (d) one or more ester linkages in the binder polymer molecule, (e)one or more ether linkages in the binder polymer molecule, (f) one or more acetal linkages in the binder polymer molecule.

According to another preferred embodiment of the present invention said hydroxy-NIPU binder (HNIPUs) involving unreacted terminal amine groups is optionally reacted with anhydride and / or epoxy and / or acid functionalities.

According to an embodiment of the present invention said binder and / or hardener sources total aromatic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product.

Said aromatic content being chemically connected with the HNIPU binder and is sourced from the groups selected from the group consisting of one or more aromatic polyamines, one or more aromatic epoxy resins, one or more epoxy functional polymers, one or more benzene ring containing polymers, one or more polyanhydrides, one or more anhydride functional polymers and combinations thereof.

According to another embodiment of the present invention said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof reveals improved drying and performance properties. Advantageously, said coat/ formulation shows fast drying system at room temperature by uniform formation of glossy filmswith hardness and scratch resistance.

According to yet another preferred embodiment of the present invention said binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binderinvolving unreacted terminal amine groups of said binder is optionally reacted with anhydride and / or epoxy and / or acid functionalities. Table 1 : Properties of Wood panels

It can therefore be inferred from Table 1 above, that both aromatic and non aromatic binder backbone can advantageously result in tack-free surfaces on wood panels when applied onto it, subject to the fulfillment of amine hydrogen equivalent wt. (AHEW) of the binder to be within the select range. However, below the select range of amine hydrogen equivalent wt. the binder remained tacky for much longer period, even beyond 100 hrs, which is less desirable.

Further, it can also be seen that curing of said binders could be effected at ambient temperatures, and as ‘m+n’ value arising out of the binder and the hardener approaches 4 (as seen in Table 2 below) the same results in a tack free ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating at about 24-100 hrs. Additionally, “m+n”>4 also advantageously allows curing at ambient to lead to tack free coating as a cured product even with monoaldehyde as hardeners.

Table 2: Properties measured on metal panels

Again, it can be further concluded from Table 2 above that there is a difference in behaviour on metal panels as compared to wood panels (Table 1 above) wherein when‘m+n’ arising out of the binder and hardener approaches 4 ambient curing sets in faster after only about 24 hrs to provide for a tack free coat. Table 3: Properties measured on metal panels

While Tables 1 and 2 above relates to improved drying properties attained, the performance properties also gets significantly enhanced. Table 4: Coating properties of cross linked HNIPUs with aldehyde and / or ketone functionalities involving different aldehyde molecules on wood panels when amine hydrogen equivalent wt. of the binder is in the range of 400 - 1600 and ‘m+ n’ >4.

Table 5: Coating properties of cross linked HNIPUs with different aldehyde molecules on metal panels when amine hydrogen equivalent wt. of the binder is in the range of 400- 1600 and ‘m+n’ >4.

5

10 It is thus possible for the present advancement to provide for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising: (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer and/or polymer, and (ii) hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being ³ 1 ,su rprisi ng ly providing said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that “m+n”>4 in said reaction product. Advantageously, a process for preparation of said coating or curable formulations thereof are also provided involving aldehyde and / or ketone functionality based hardening/ cross linking at room temperature for ambient curing and film forming, wherein said coats/films are found to have improved drying and performance properties.

Claims

We Claim :

1. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising:

(l! wherein: n³ 2; x= 0-4;

R₁ R₂,R3, and R₅comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;

(ii) hardener comprising“m” number of aldehyde and / or ketone functionalities, “m” being >1, adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that“m+n”>4 in said reaction product.

2. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof as claimed in claim 1 wherein said“m” number of aldehyde and/or ketone functionality based hardeners comprise selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.

3. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof as claimed in claim 1 which is either a coating comprising ambient cured reaction product of said (i) and (ii), or, is a formulation comprising ambient curable ready to apply said (i) and (ii) as components of a formulation favouring generation of said reaction product based coating.

4. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof as claimed in claim 1 having said binder and / or hardener sourced total aromatic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product.

5. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coatingor curable formulations thereof as claimed in claim 4 wherein said aromatic contentis chemically connected with the HNIPU binder and is sourced from the groups selected from the group consisting of one or more aromatic polyamines, one or more aromatic epoxy resins, one or more epoxy functional polymers, one or more benzene ring containing polymers, one or more polyanhydrides, one or more anhydride functional polymers and combinations thereof.

6. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof as claimed in claim 1 wherein

said hardener comprises“m” number of aldehydeand/ or ketone functionalities; and said binder base comprises amines and/or imine reacted polycyclic carbonate and/or cyclic carbonate based (HNIPU) binder, said polycyclic carbonate and/or cyclic carbonate includes reaction products of at least one aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

7. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof as claimed in claim6 wherein said hardener comprises aldehyde functionality based aldehyde compound such that “m” >1 including aqueous, non-aqueous, neat liquid and solvent-borne polyaldehydes comprising acetal adduct of polyaldehyde and alcohols/glycols, schiff base adduct of polyamine/polyimine and polyaldehyde having “m” number of free aldehyde functionalities per adduct molecule including alkyl, aryl or aliphatic, cyclo aliphatic radicals that may include 1-30 or higher carbon atoms, linear and/or branched moieties, one or more hetero atoms containing functionality and includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; PARALOID™ EDGE XL-195 is a 1 ,4-cyclohexanedicarboxaldehyde; 3,4- Dimethoxybenzaldehyde; croton-aldehyde, Polysaccharide aldehydes, n- butyraldehyde, benzaldehyde, aromatic aldehydes include benzaldehyde, ortho-, para- and meta-tolualdehyde, anisaldehyde and substituted benzaldehydes having one to three substituents and wherein the substituents are selected from lower alkyl, methoxy, mono- and di- alky Iasi no, amino, nitro or halogen, m- hydroxy-benzaldehyde, 1 ,4-hydroxynaphthaldehyde, 3-

Climethylaminobenzaldehyde,4-hydroxy3-methoxybenzaldehyde, I (3 formylphenyl) 3- methyl-S-pyrazolone, I (4 formylphenyl) 3 methyl-5 pyrazolone and 1 -(2-formylphenyl) 3-methyl-5-pyrazolone, o-, m-, and p- acetoacetaminobenzaldehyde, 3--brom-2-hydroxybenzaldehyde, 2 hydroxy 3 nitrobenzaldehyde, 6 hydroxy-2-methylbenzaldehyde, and 2-hydroxy-5- methylbenzaldehyde, Glyoxal solution 40 wt. % in H20, Glyceraldehyde, 4- Bromothiazole-2-carboxaldehyde, 2- Imidazolecarboxaldehyde, 5 -Nitro- 2- furaldehyde, 5-Formyluracil, 3- Furancarboxaldehyde , 3-

Thiophenecarboxaldehyde , Furfural , Pyrrole-2-carboxaldehyde , Glutaraldehyde solution 50 wt. % in FI20, Tetrahydrofuran-3-carboxaldehyde solution 50 wt. % in FI20, 2,3-Thiophenedicarboxaldehyde, 2,3,4,5,6-Pentafluorobenzaldehyde, 2,3,6-Trichlorobenzaldehyde, Fyrrole-2-carboxaldehyde, 2,4-

Dihydroxybenzaldehyde,4-bromo-2-cyanobenzaldehyde,3-Chloro-5- (trifluoromethyl)benzaldehyde,lsophthalaldehyde,Phthaldialdehyde,

Terephthal aldehyde, 4- Fluoro-3-methoxybenzaldehyde, p- Anisaldehyde,3- Bromo-5-(trifluoromethyl)benzaldehyde, 4- Methyl-S it rif I uorom ethyl) benzaldehyde, 1,1'-

Ferrocenedicarboxaldehyde,cyclicpolyaldehydesare trans-1 ,3- cyclohexanedicarboxaldehyde; cis- 1 ,3-cyclohexanedicarboxaldehyde; trans- 1,4- cyclohexanedicarboxaldehyde;cis-1 , 4-cyclohexanedicarboxaldehyde; a mixture of 1 ,3-cyclohexanedicarboxaldehydes and 1 ,4-cyclohexanedicarboxaldehydes, exo,exo- 2,5-norbomanedicarboxaldehyde; exo,exo-2,6- norbornanedicarboxaldehyde; exo,endo- 2,5-norbomanedicarboxaldehyde; exo,endo-2,6-norbornanedicarboxaldehyde; endo, endo- 2,5- norbomanedicarboxaldehyde; endo,endo-2,6-norbornanedicarboxaldehyde product (endo and exo mixture); 3-(3-formylcyclohexyl)propanal;3-(4- formylcyclohexyl)propanal;2-(3-formylcyclohexyl)propanal; 2-(4- formylcyclohexy propanal; cyclododecane-1 ,4,8-tricarbaldehyde, preferably includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; paraloid™ edge xl-195 (1 , 4-cyclohexanedicarboxaldehyde) ; 3,4-

Dim ethoxy benzaldehyde.

8. Ambient cured hydroxyl non-isocyanate polyurethane ( HN I PU) based coating or formulations thereof as claimed in claim 6 wherein said hardener comprises at least one or more ketone functionality based ketone compound such that “m” > 1 including mono-, d i- , tri- and poly-ketone compounds, said monoketones including Methyl isobutyl ketone, Dicyclohexyl ketone, Methyl 2-pyrrolyl ketone, 2-Furyl methyl ketone, Cyclohexyl phenyl ketone, 3-Hepten-2-one, Ethyl vinyl ketone, Di(2- py ridy I) ketone, Po I y ( v i n y I methyl ketone), Bis(1 -methyl-2- imidazolyl)ketone, Di-2-thienyl ketone, 1 - Isoquinolinyl phenyl ketone, Diethyl ketone, Diisobutyl ketone, Ethyl methyl ketone, Isopropyl methyl ketone, Methyl propyl ketone, Benzophenone, Acetophenone, Butyrophenone, 2', 5'- Dihydroxyacetophenone, 2-Heptanone, 2,4-Dimethyl-3-pentanone, 4- Methoxyphenylacetone, 2- Acetylpyrrole, 2- Acetylpyridine, 3-

Nonanone sovalerophenone, 1 ,3- Diphenyl-2-propanone, 2-Aminobenzophenone, 3- Acetylindole, 2- Acetyl-5-chlorothiophene, 2-Benzoylpyridine, 2,2,2- Tri phenyl acetophenone, Benzylideneacetone, Dipyridin-4-ylmethanone, HEPTADECYL 2- NAPHTHYL KETONE, Xanthone, 2' - Am inoacetophenone, 2- Chloroacetophenone, 4,4'-Dichlorobenzophenone, 9- Acetylanthracene, 4,4'- Difluorobenzophenone,Tetraphenylcyclopentadienone, 2- Isopropyl -5- methylcyclohexanone, 9( 10H) -Anthracenone, Isophorone, 1 -Dimethylamino-2- propanone, 3-Amino-2-cyclohexen- 1 - on e, Dici n n am al acetone, ( Diethyl ami no) acetone, 4- Am ino-9-fluorenone,Hexaketocyclohexaneoctahydrate,

Acetone, 2- Acetylpyrazine, 3- Acetyl-2,4 -dim ethylpyrrole,Acetylpyrazine,Furoin, Cyclohexanone, 1 ,1'-Carbonyldiimidazole, 2' -Hydroxyacetophenone,

Methylglyoxal 1,1 -dimethyl acetal, 4-Methylbenzophenone, 1,1- Dichloro-2- propanone, Benzophenone-3,3' ,4,4' -tetracarboxylic dianhydride, 3-Hydroxy-1 ,2- dimethyl-4(1 H)-pyridone, Ethyl 2-oxo- 1 -cyclooctanecarboxylate, 1-Methyl-2- pyrrolidinone,1 - Benzyl -2- pyrrol id i none, N- Met hylpyrro lido ne, 4- Hydroxy- 4- methyl - 2-pentanone; 2,2,6,6-Tetramethyl-4-piperidone,Diacetone amine Triacetone amine, ACETYLACETONE IMIDE;

said Di-ketones including 1 ,3- Dibenzoylpropane ,1,2-diketone (diacetal), 1,3- diketone (acetylacetone) , 15,4-diketone (hexane-2, 5-dione), 1,2-

Naphthoquinone, 2-Methyl-1 , 4- naphthoquinone, 1 ,3- Dibenzoylbenzene, 2- Acetylcyclopentanone,4-Cyclopentene-1 ,3-dione, 4,5-DICHLORO-4-

( Bl S( ETHOXYCARBONYL) METHYL) - 1 ,2- NAPHTHOQUI NONE; said triketone including 2-acetyl-1 -methoxy-anthraquinone, cycloheximide, actiphenol;

said polyketones including Po I y ( v i n y I methyl ketone), polyketones,

Polyvinylpyrrolidone, polyether etherketone(PEEK).

9. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof as claimed in claim 6 wherein said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1 ,6-hexamethylene diamine; 1 ,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine) ; 2- methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramine Jeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1 ,3-propanediamine, bis- (4,4’-am inocyclo hexyljmethane, tricyclodecanediamine (or 3(4), 8(9) -bis-

(aminomethyl)tricyclo [5 .2 .I . I0]decane; 2-methylpentane-1 ,5-diamine; octylamine and hexylamine; polyalkylenam ines such as diethylenetriamine, triethylenetetram ine, tetraethylenepentam ine, pentaethylenehexamine, propylenediamine, dipropylenetriam ine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trim ethylhexam ethylenediam ine, N,N’-bis-(3 -am inopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediam ine, 1,3- diaminopentane, and hexamethylenediamine; cycloaliphatic amines such as 1, 2- or 1,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino- 4-ethylcyclohexane; 1 ,4-diamino-3, 6-diethyl-cyclohexane, 1 -cyclohexyl-3, 4- diaminocyclohexane; 4,4’-diaminodicyclohexylmethane, propane, 2,2-bis-(4- aminocyclohexylj-methane and -pro pane, 3,3’-dimethyl-4,4’- diaminodicyclohexyl-methane, 3-amino-1 -cyclohexylaminopropane, 1,3- and 1,4- bis (amininomethyl)-cyclohexane; polyoxyalkylenaminessuchas poly (oxy ethylenediam ine), poly(oxyethylenetriamine), poly(oxypropylenediam ine) , and poly (oxypropylenetriamine); heterocyclic amines such as N-am inoethylpiperazine and 1 ,4-bis-(3’-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3- aminopropyltriethoxysilane;polyethyleneglycol monoamine, 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

10. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof as claimed in claim 6 wherein said cyclic ether precursors to polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly- glycidyl terminated polyether oligomers/ polymers thereof.

11. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof as claimed in claim 6 wherein said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerinecarbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl) - ethylene carbonate, 3, 4-0-isopropylidene-D-mannitol-1 ,2:5, 6-dicarbonate and D-mannitol-1 ,2:5, 6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-

1.3-dioxolan-2-one, 4-Trifluoromethyl-1 ,3-dioxolan-2-one, bisphenol A polycarbonate, Divinylbenzene Dicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate-modified bis(4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane compound, trimethylolpropanetricyclocarbonate, chlorine- contained aliphatic tricyclocarbonates, 2-oxo-1 ,3-dioxolan-4-yl) methyl N-allyl carbamate, 4-(2-oxo-

1.3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxymethyl)-1 ,3-dioxolan-2- one, (2-oxo-1 ,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscycliccarbonates, 4-(2-oxo-1 ,3-dioxolan-4-yl)butyl N- dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4- glycidyloxy phenyl)phenyl phosphine oxide (BGPPO), and poly( propy leneg lycol) dig lycidy I ether, Rosin based Cylic carbonate, Cyclic bis- carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl) 1 ,3-dioxolan-2- one, and is preferably jeffsol® glycerine carbonate.

12. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof as claimed in claim 1 adapted for clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

13. A method of providing ambient cured hydroxyl non-isocyanate polyurethane

(HNIPU) based coating or curable formulations thereof said method comprising: a) having a binder base comprising (i) ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of amine hydrogen equivalent weight in the range of 400-1600 and having the following structures (I) below

wherein: n> 2; x = 0-4;

R₁ R₂,R3, and R₅ comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties; R₄ comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; b) having a hardener comprising “m” number of aldehyde and / or ketone functionalities,“m” being > 1 ; c) mixing said binder (a) with said hardener(b) and allowing the mixture to dry at ambient temperature of -5 to 40 °C to provide for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (a) and (b) such that m+n>4 in said reaction product.

14. A method as claimed in claim 13 wherein said step (b) of having a hardener comprises having “m” number of aldehyde and / or ketone functionality based hardeners including selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.

15. A method as claimed in claim 13 wherein said binder and / or hardener sources total aromatic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product.

16. A method as claimed in claim 13 wherein said step (a) of having a binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder includes reacting polycyclic carbonate and/or cyclic carbonate with amines and/or imines in stoichiometric equivalents in the range from 1:0.4 to 1:2.2 respectively to yield a polymer with hydroxyurethane (PHU) groups having amine equivalent weight in the selective range of 400-1600.

17. A method as claimed in claim 16 wherein said polycyclic carbonate and/or cyclic carbonate is sourced from reactions between aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

18. A method as claimed in claim 16 wherein said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerinecarbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl) - ethylene carbonate, 3, 4-0-isopropylidene-D-mannitol-1 ,2:5, 6-dicarbonate and D-mannitol-1 ,2:5, 6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-

1.3-dioxolan-2-one, 4-Trifluoromethyl-1 ,3-dioxolan-2-one, bisphenol A polycarbonate, Divinylbenzene Dicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate-modified bis(4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane compound, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, 2-oxo-1 ,3-dioxolan-4-yl) methyl N-allyl carbamate, 4-(2-oxo-

1.3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxymethyl)-1 ,3-dioxolan-2- one, (2-oxo-1 ,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscyclic carbonates, 4-(2-oxo- 1 ,3-dioxolan-4-yl)butyl N-dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4-glycidyloxy phenyl)phenyl phosphine oxide (BGPPO), and poly ( p ropy I eneg ly col ) d ig ly cidy I ether, Rosin based Cylic carbonate, Cyclic bis-carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine- contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl) 1 ,3-dioxolan-2- one, and is preferably jeffsol® glycerine carbonate.

19. A method as claimed in claim 16 wherein said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1 ,6-hexamethylene diamine; 1 ,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine) ; 2- methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1 ,3-propanediamine, bis-(4,4’- aminocyclo hexyl)methane, tricyclodecanediamine (or 3(4), 8(9)-bis-

(aminomethyl)tricyclo [5 .2 .I . I0]decane; 2-methylpentane-1 ,5-diamine; octylamine and hexylamine; polyalkylenam ines such as diethylenetriamine, triethylenetetram ine, tetraethylenepentam ine, pentaethylenehexamine, propylenediamine, dipropylenetriam ine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trim ethylhexam ethylenediam ine, N,N’-bis-(3 -am inopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediam ine, 1,3- diaminopentane, andhexamethylenediam ine; cycloaliphatic amines such as 1,2- or 1 ,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino- 4-ethylcyclohexane; 1 ,4-diamino-3, 6-diethyl-cyclohexane, 1 -cyclohexyl-3, 4- diaminocyclohexane; 4,4’-diaminodicyclohexylmethane, propane, 2,2-bis-(4- aminocyclohexyl)-methane and -pro pane, 3,3’-dimethyl-4,4’- diaminodicyclohexyl-methane, 3-amino-1 -cyclohexylaminopropane, 1,3- and 1,4- bis (amininomethyl)-cyclohexane; polyoxyalkylenam ines such as poly (oxy ethylenediam ine), poly(oxyethylenetriamine), poly(oxypropylenediam ine) , and poly (oxypropylenetriamine); heterocyclic amines such as N-am inoethylpiperazine and 1 ,4-bis-(3’-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3-aminopropyltriethoxysilane; polyethyleneglycol monoamine, 3-am inopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

20. A method as claimed in claim 16 wherein said cyclic ether precursors for generation of polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/polymers thereof.

21. A method as claimed in claim 13 wherein said hardener comprises aldehyde functionality based aldehyde compound such that “m”> 1 including aqueous, non- aqueous, neat liquid and solvent-borne polyaldehydes comprising acetal adduct of polyaldehyde and alcohols/glycols, schiff base adduct of polyamine/polyimine and polyaldehyde having “m” number of free aldehyde functionalities per adduct molecule including alkyl, aryl or aliphatic, cyclo aliphatic radicals that may include

1-30 or higher carbon atoms, linear and/or branched moieties, one or more hetero atoms containing functionality and includes 3-4 dimethoxy benzaldehyde,

2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; PARALOID™ EDGE XL-195 is a 1 ,4-cyclohexanedicarboxaldehyde; croton-aldehyde, Polysaccharide aldehydes, n-butyraldehyde, benzaldehyde, aromatic aldehydes include benzaldehyde, ortho-, para- and meta-tolualdehyde, anisaldehyde and substituted benzaldehydes having one to three substituents and wherein the substituents are selected from lower alkyl, methoxy, mono- and di-alkylasino, amino, nitro or halogen, m-hydroxy-benzaldehyde, 1 ,4-hydroxynaphthaldehyde, 3- Climethylaminobenzaldehyde,4-hydroxy3-methoxybenzaldehyde, I (3 formylphenyl) 3- methyl-S-pyrazolone, I (4 formylphenyl) 3 methyl-5 pyrazolone and 1 -(2-formylphenyl) 3-methyl-5-pyrazolone, o-, m-, and p- acetoacetaminobenzaldehyde, 3--brom-2-hydroxybenzaldehyde, 2 hydroxy 3 nitrobenzaldehyde, 6 hydroxy-2-methylbenzaldehyde, and 2-hydroxy-5- methylbenzaldehyde, Glyoxal solution 40 wt. % in H20, Glyceraldehyde, 4- Bromothiazole-2-carboxaldehyde, 2- Imidazolecarboxaldehyde, 5 -Nitro- 2- furaldehyde, 5- Formyluracil, 3- Furancarboxaldehyde , 3-

Thiophenecarboxaldehyde , Furfural , Pyrrole-2-carboxaldehyde , Glutaraldehyde solution 50 wt. % in H20, Tetrahydrofuran-3-carboxaldehyde solution 50 wt. % in H20, 2,3-Thiophenedicarboxaldehyde , 2, 3, 4, 5, 6- Pentafluorobenzaldehyde, 2,3,6-Trichlorobenzaldehyde, Pyrrole-2-carboxaldehyde, 2,4-

Dihydroxybenzaldehyde, 4-bromo-2-cyanobenzaldehyde, 3-Chloro-5-

( trif I uorom ethyl) benzaldehyde, lsophthalaldehyde,Phthaldialdehyde,

Terephthalaldehyde, 4- Fluoro-3-methoxybenzaldehyde, p-

An isaldehyde,3-Bromo- 5- (trifluorom ethyl) benzaldehyde, 4-Methyl-3- (trifluoromethyl) benzaldehyde, 1 ,1'-Ferrocenedicarboxaldehyde, cyclicpolyaldehydes are trans- 1 ,3-cyclohexanedicarboxaldehyde; cis-1,3- cyclohexanedicarboxaldehyde; trans- 1 ,4-cyclohexanedicarboxaldehyde; cis-1, 4- cyclohexanedicarboxaldehyde; a mixture of 1 ,3-cyclohexanedicarboxaldehydes and 1 ,4-cyclohexanedicarboxaldehydes, exo,exo- 2,5- norbomanedicarboxaldehyde; exo,exo-2,6-norbornanedicarboxaldehyde; exo,endo-2,5-norbomanedicarboxaldehyde; exo,endo-2,6- norbornanedicarboxaldehyde; endo, endo-2,5-norbomanedicarboxaldehyde; endo,endo-2,6-norbornanedicarboxaldehyde product (endo and exo mixture); 3- (3-formylcyclohexyl)propanal;3-(4-formylcyclohexyl) propanal; 2-(3- formylcyclohexyl) propanal; 2-(4-formylcyclohexyl)propanal; cyclododecane- 1 ,4,8-tricarbaldehyde, preferably includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde;paraloid™ edge xl-195 (1,4- cyclohexanedicarboxaldehyde) ; 3,4-Dimethoxybenzaldehyde.

22. A method as claimed in claim 13 wherein said hardener comprises at least one or more ketone functionality based ketone compound such that “m” >1 including mono-, d i - , tri- and poly-ketone compounds, said monoketones including Methyl isobutyl ketone, Dicyclohexyl ketone, Methyl 2-pyrrolyl ketone,

2-Furyl methyl ketone, Cyclohexyl phenyl ketone, 3-Flepten-2-one, Ethyl vinyl ketone, Di ( 2- py r idy I ) ketone, Po I y ( v i n y I methyl ketone), Bis(1 -methyl-2- imidazolyl)ketone, Di-2-thienyl ketone, 1 - Isoquinolinyl phenyl ketone, Diethyl ketone, Diisobutyl ketone, Ethyl methyl ketone, Isopropyl methyl ketone, Methyl propyl ketone, Benzophenone, Acetophenone, Butyrophenone, 2', 5'-

Dihydroxyacetophenone, 2-Fleptanone, 2,4-Dimethyl-3-pentanone, 4- Methoxyphenylacetone, 2- Acetylpyrrole, 2- Acetylpyridine, 3-

Nonanone sovalerophenone, 1 ,3- Diphenyl-2-propanone, 2-Aminobenzophenone, 3- Acetylindole, 2- Acetyl-5-chlorothiophene, 2-Benzoylpyridine, 2,2,2- Triphenylacetophenone, Benzylideneacetone, Dipyridin-4-ylmethanone,

HEPTADECYL 2- NAPHTHYL KETONE, Xanthone, 2' - Am inoacetophenone, 2- Chloroacetophenone, 4,4'-Dichlorobenzophenone, 9- Acetylanthracene, 4,4'- Difluorobenzophenone,Tetraphenylcyclopentadienone, 2- Isopropyl -5- methylcyclohexanone, 9( 10H) -Anthracenone, Isophorone, 1 -Dimethylamino-2- propanone, 3-Amino-2-cyclohexen- 1 - on e, Dici nn am al acetone,

( Diethyl ami no) acetone, 4- Am ino-9-fluorenone,Hexaketocyclohexaneoctahydrate, Acetone, 2- Acetylpyrazine, 3- Acetyl-2,4 -dim ethylpyrrole,Acetylpyrazine,Furoin, Cyclohexanone, 1 ,1'-Carbonyldiimidazole, 2' -Hydroxyacetophenone,

Naphthoquinone, 2-Methyl-1 , 4- naphthoquinone, 1 ,3- Dibenzoylbenzene, 2-

Acetylcyclopentanone,4-Cyclopentene-1 ,3-dione, 4,5-DICHLORO-4-

( Bl S( ETHOXYCARBONYL) METHYL) - 1 ,2- NAPHTHOQUI NONE;

said triketone including 2-acetyl-1 -methoxy- ant h raq u i non e,cycloh ex im ide, act i phenol;

said polyketones including Po I y ( v i n y I methyl ketone), polyketones, Polyvinylpyrrolidone, polyether etherketone(PEEK) .

23. A method as claimed in claim 13 providing for ambient cured hydroxyl non isocyanate polyurethane (HNIPU) based coating or curable formulations thereof as clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

24. A method of delivering ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof, said method comprising: i. Having a base binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having the following structure (I) below

wherein: n³ 2; x = 0-4;

R₁ R₂,R3, and R₅ comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties; R₄ comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and

ii. Having a hardener comprising “m” number of aldehyde and / or ketone functionalities,“m” being > 1

iii. Mixing said binder base (i) with said hardener (ii); and

25. A method of delivering ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating as claimed in claim 24 wherein said hardener of step (ii) comprises said “m” number of aldehyde and/or ketone functionality based hardeners comprising selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.

26. A method of delivering as claimed in claim 24 wherein said substrates include Metal, Wood, Plastic, Aluminum, Glass, Paper, Gypsum, Cement, Porus bricks, Sand, and wherein said method includes either delivering the coating directly on any of these substrates or on top of a suitable primer, and also includes top-coating said coating with any other type of binder said coating provided as a topcoat or undercoat being either a clear-coat or a pigmented coat.

27. A method of delivering as claimed in claim 24 wherein said applying the coating includes applying by brush, spray, roller, spin coater, bar coater, applicator, poring, impregnating, dipping in resin, wounding of solid resin on said substrate.