Claims:We Claim:

1. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coatingor curableformulations 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 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;
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) 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 functionalitybased hardeners comprise selectively at least one aldehydecompound, 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 includingaqueous, 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-alkylasino, amino, nitro or halogen, m-hydroxy-benzaldehyde, 1,4-hydroxynaphthaldehyde, 3-Climethylaminobenzaldehyde,4-hydroxy3-methoxybenzaldehyde, l (3 formylphenyl) 3- methyl-S-pyrazolone, l (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 H2O, 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 H2O, Tetrahydrofuran-3-carboxaldehyde solution 50 wt. % in H2O, 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,Isophthalaldehyde,Phthaldialdehyde, Terephthalaldehyde, 4-Fluoro-3-methoxybenzaldehyde, p-Anisaldehyde,3-Bromo-5-(trifluoromethyl)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-Dimethoxybenzaldehyde.

8. Ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) 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-, di-, 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-pyridyl) ketone, Poly(vinyl 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,Isovalerophenone, 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'-Aminoacetophenone, 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-one,Dicinnamalacetone, (Diethylamino)acetone, 4-Amino-9-fluorenone,Hexaketocyclohexaneoctahydrate, Acetone, 2-Acetylpyrazine, 3-Acetyl-2,4-dimethylpyrrole,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(1H)-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 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-Indandione, 4-Cyclopentene-1,3-dione,Hulupinic acid,Anthraquinone,Octafluoroanthraquinone,Acetylacetone,1-(4-MORPHOLINYLACETYL)-2-PYRROLIDINONE,Glutarimide, 4-(BIS(ETHOXYCARBONYL)METHYL)-1,2-NAPHTHOQUINONE;
said triketone including 2-acetyl-1-methoxy-anthraquinone, cycloheximide, actiphenol;
said polyketones including Poly(vinyl 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, 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 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 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-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(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethylpiperazine 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-O-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(propyleneglycol)diglycidyl 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

(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 moietiescontaining 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 aldehydecompound, ketone compound, compounds with both aldehyde and keto functionality.

15. A method as claimed in claim 13 whereinsaid 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 reactingpolycyclic 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) groupshaving 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-O-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(propyleneglycol)diglycidyl 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 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 1,3-diaminopentane, andhexamethylenediamine; 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; polyoxyalkylenamines such as poly(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethylpiperazine 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).

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, l (3 formylphenyl) 3- methyl-S-pyrazolone, l (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 H2O, 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 H2O, Tetrahydrofuran-3-carboxaldehyde solution 50 wt. % in H2O, 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, Isophthalaldehyde,Phthaldialdehyde, Terephthalaldehyde, 4-Fluoro-3-methoxybenzaldehyde, p-Anisaldehyde,3-Bromo-5-(trifluoromethyl)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” =1including mono-, di-, 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-pyridyl) ketone, Poly(vinyl 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,Isovalerophenone, 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'-Aminoacetophenone, 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-one,Dicinnamalacetone, (Diethylamino)acetone, 4-Amino-9-fluorenone,Hexaketocyclohexaneoctahydrate, Acetone, 2-Acetylpyrazine, 3-Acetyl-2,4-dimethylpyrrole,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(1H)-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 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-Indandione, 4-Cyclopentene-1,3-dione,Hulupinic acid,Anthraquinone,Octafluoroanthraquinone,Acetylacetone,1-(4-MORPHOLINYLACETYL)-2-PYRROLIDINONE,Glutarimide, 4-(BIS(ETHOXYCARBONYL)METHYL)-1,2-NAPHTHOQUINONE;
said triketone including 2-acetyl-1-methoxy-anthraquinone,cycloheximide,actiphenol;
said polyketones including Poly(vinyl 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

(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 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 coatingupon drying at ambient temperature of -5 to 40oC based on generation of a reaction product having m+n =4 in said reaction product.

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, spincoater, bar coater, applicator, poring, impregnating, dipping in resin, wounding of solid resin on said substrate.

Dated this the 15th day of January, 2018 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
, Description:FIELD OF THE INVENTION

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, themanufacture of conventional polyurethane process hastheir 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 80oC 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 carbonatedsoybean oil) by reacting carbon dioxide with an epoxidized vegetable oil. The carbonated vegetable oils are advantageously used therein forproducing 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 providinga cyclic carbonate, an amine, and a cooperative catalyst system that has aLewis acid and a Lewis base.
Literature publicationson ‘Solubility in CO2 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 compositioncontainingpolycarbamate and aldehyde cross linker and acid catalyst.
US4520167discloses 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 mixture of the latter with an epoxy resin, with a hardener bearing amino groups.
Reference to prior arts is also drawn to the use of aldehydes as cross-linking agents:wherein CN 102093873 discloses a fracture liquidhaving the advantages of good thermal stability, salt resistance, and shear resistance, and can avoid residual slag of polymer chain groupconsisting of synthetic polymer 0.1-1, crosslinking agent 0.1-1, clay stabilizer 0.2-1, surfactant 0.1-0.8, oxidant 0.001-0.05, and H2O 94-99% wherein the synthetic polymer is homopolymer and polymer prepared from acrylamide monomer, vinyl monomer, and hydrophobic monomer, and its mol. wt. is 500000-10000000 and the crosslinking agent is organic amphoteric metal complex crosslinking agent and/or aldehyde crosslinking agent.
DE2911062 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 polyhydroxycompounds.Aldehydes crosslink with cellulosic polyols at high temperature is disclosed.
GB807851 teaches heat-resistant phenolic resins prepared by forming the polybasic inorganic acid partial ester of a polyhydroxy aromatic compound having an unsubstituted position reactive with HCHO by reaction with H3BO4, H3PO4, or POCl3 with heating in such a manner that a substantial proportion of the phenolic OH groups remains unreacted, and then curing at an elevated temperature with an aldehyde or compound that decomposes to an aldehyde takes place.
FR1478229 discloses urethane methylol ethers containing free OH groups prepared by treating ß-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 ß-hydroxyethyl methoxymethyl carbamate, MeOCH2NHCO2CH2CH2OH, which on treatment with HCHO gave methylene bis (ß-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 INVENTION

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 thereofwhich 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 groupsand 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 formulationsas 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 INVENTION

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, oxanesbased 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-alkylasino, amino, nitro or halogen, m-hydroxy-benzaldehyde, 1,4-hydroxynaphthaldehyde, 3-Climethylaminobenzaldehyde,4-hydroxy3-methoxybenzaldehyde, l (3 formylphenyl) 3- methyl-S-pyrazolone, l (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 H2O, 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 H2O, Tetrahydrofuran-3-carboxaldehyde solution 50 wt. % in H2O, 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,Isophthalaldehyde,Phthaldialdehyde, Terephthalaldehyde, 4-Fluoro-3-methoxybenzaldehyde, p-Anisaldehyde,3-Bromo-5-(trifluoromethyl) 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-Dimethoxybenzaldehyde.

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-, di-, 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-pyridyl) ketone, Poly(vinyl 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,Isovalerophenone, 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'-Aminoacetophenone, 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-one,Dicinnamalacetone, (Diethylamino)acetone, 4-Amino-9-fluorenone,Hexaketocyclohexaneoctahydrate, Acetone, 2-Acetylpyrazine, 3-Acetyl-2,4-dimethylpyrrole,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(1H)-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 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-Indandione, 4-Cyclopentene-1,3-dione,Hulupinic acid,Anthraquinone,Octafluoroanthraquinone,Acetylacetone,1-(4-MORPHOLINYLACETYL)-2-PYRROLIDINONE,Glutarimide, 4-(BIS(ETHOXYCARBONYL)METHYL)-1,2-NAPHTHOQUINONE;
said triketone including 2-acetyl-1-methoxy-anthraquinone, cycloheximide, actiphenol;
said polyketones including Poly(vinyl 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 hexyl)methane, tricyclodecanediamine (or 3(4), 8(9)-bis-(aminomethyl)tricyclo [5 .2 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 1,3-diaminopentane, andhexamethylenediamine; 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(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), 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-aminopropyltrimethoxysilane, 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® glycerinecarbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl)-ethylene carbonate, 3,4-O-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, 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 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(propyleneglycol)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-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

(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;

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 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 in said method 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.

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 precursors 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-O-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,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 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(propyleneglycol)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-dioxolan-2-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 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 1,3-diaminopentane, andhexamethylenediamine; 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(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethylpiperazine 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).

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 di-alkylasino, amino, nitro or halogen, m-hydroxy-benzaldehyde, 1,4-hydroxynaphthaldehyde, 3-Climethylaminobenzaldehyde,4-hydroxy3-methoxybenzaldehyde, l (3 formylphenyl) 3- methyl-S-pyrazolone, l (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 H2O, 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 H2O, Tetrahydrofuran-3-carboxaldehyde solution 50 wt. % in H2O, 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,Isophthalaldehyde,Phthaldialdehyde, Terephthalaldehyde, 4-Fluoro-3-methoxybenzaldehyde, p-Anisaldehyde,3-Bromo-5-(trifluoromethyl)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-Dimethoxybenzaldehyde.

According to another preferred aspect of said method said hardener comprises at least one or more ketone functionality based ketone compound such that “m” =1including mono-, di-, 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-pyridyl) ketone, Poly(vinyl 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,Isovalerophenone, 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'-Aminoacetophenone, 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-one,Dicinnamalacetone, (Diethylamino)acetone, 4-Amino-9-fluorenone,Hexaketocyclohexaneoctahydrate, Acetone, 2-Acetylpyrazine, 3-Acetyl-2,4-dimethylpyrrole,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(1H)-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 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-Indandione, 4-Cyclopentene-1,3-dione,Hulupinic acid, Anthraquinone, Octafluoroanthraquinone, Acetylacetone, 1-(4-MORPHOLINYLACETYL)-2-PYRROLIDINONE, Glutarimide, 4-(BIS(ETHOXYCARBONYL)METHYL)-1,2-NAPHTHOQUINONE;
said triketone including 2-acetyl-1-methoxy-anthraquinone, cycloheximide, actiphenol;
said polyketones including Poly(vinyl 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

(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 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 40oC 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.

DETAILED DESCRIPTION OF THE PRESENT INVENTION
As discussed hereinbefore, the present invention provides for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curableformulations 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 curingor 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(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 moietiescontaining 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and

Said select hardenercomprises“m” number of aldehyde and/ or ketone functionalities, “m” being =1 and upon mixing said binder (I) with said hardener andfurther allowingthe 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 functionalitybased hardeners comprise selectively at least one aldehydecompound, ketone compound, compounds with both aldehyde and keto functionality.

More preferably saidambient 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, saidambient 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.

Also 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 HNIPUs oligomer/ polymer comprising select binder functionalities of selective amine content together with select hydroxyurethane repeat units in said NIPHU oligomer/ polymer; further providing a hardener comprising aldehyde and/ or ketone functionalities; mixing said binder with said hardener 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.

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

The select binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) 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 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.

According to an embodiment of the present invention 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.

According to an embodiment of the present invention the ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising said hydroxy-NIPUs (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 thereofreveals 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
After 4 Hr After 24 Hr After 100 Hr
Sample No Backbone AHEW Tackfree Tackfree Tackfree
1 Without aromatic 1140 NO YES YES
2 with aromatic 1200 Yes YES YES
3 1971 NO NO NO
4 1800 NO NO NO
5 300 NO NO YES
6 m+n<4 (glycerol carbonate with IPDA backbone reaction product as binder; cured with glyoxal as dialdehyde hardener) 1200 NO NO YES
7 m+n<3 (glycerol carbonate with IPDA backbone reaction product as binder; cured with acetone as monoketone hardener) 1200 NO NO YES

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

After 4 Hr After 24 Hr After 100 Hr
Sample No Backbone AHEW Tackfree Tackfree Tackfree
1 Without aromatic 1140 NO YES YES
2 with aromatic 1200 Yes YES YES
3 1971 NO NO YES
4 1800 NO NO YES
5 300 NO YES YES
6 m+n<4 (glycerol carbonate with IPDA backbone reaction product as binder; cured with glyoxal as dialdehyde hardener) 1200 NO YES YES
7 m+n<3 (glycerol carbonate with IPDA backbone reaction product as binder; cured with acetone as monoketone hardener) 1200 NO NO NO

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 hrsto provide for a tackfree coat.

Table 3: Properties measured on metal panels
Gloss Koning Hardness Scratch Hardness
20° 60° 85°
Without aromatic 37 80.7 70.6 14 1100
with aromatic 45.8 91.4 87.9 17 1200

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.
Measurements of properties on wood panels
Cross linker Drying time ON WOOD Pendulum Hardness (persoz )
1 hr 4 hr 12 hr 24 hr 7 days
1. Glyoxal 40 % 30 min 43 53 104 120 170
2. 2, 5-Diformylfuron 30 min 82 82 90 113 175
3. Furfural 40 min 55 54 72 83 138
4. Glutaraldehyde 35 min 28 31 66 89 152
5. 4, 5 dimethyl 2-furaldehyde 30 min 33 34 79 101 139
6. 1, 4-cyclohexanedicarboxaldehyde (DOW) 60 min 30 37 77 80 132

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.
Measurements on Metal panels
Cross linker Drying time Pendulum Hardness(persuz) Scratch resistance
1 hr 4 hr 12 hr 24 hr 7 days 1 hr 4 hr 12 hr 24 hr 7 days
1. Glyoxal 40 % 20 min 36 39 80 108 500 500 800 900 1800
2. 2, 5 Diformylfuron 20 min 97 103 105 103 400 400 600 700 1000
3. Furfural 20 min 33 38 59 83 500 500 600 700 1300
4. Glutaraldehyde 20 min 26 31 60 61 500 500 700 600 1400
5. 4, 5 dimethyl 2-furaldehyde 30 min 23 24 48 53 300 400 700 700 1200
6. 1,4-cyclohexanedicarboxaldehyde(DOW) 60 min 24 24 65 71 300 400 800 800 1000

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 =1,surprisingly 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 curableformulations thereofare 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.