Claims:We Claim:
1. A binder with hydroxyl non-isocyanate polyurethane (HNIPU) backbone comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block represented by the following structure

wherein: m=2,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
wherein in said binder the pendant carbamate pendant from and adjacent to urethane repeat unit of said HNIPU backbone is a result of urea reacted secondary hydroxyl groups sourced of said omega(?)-hydroxycarbamate repeat units on said HNIPU backbone favouring at least one urea terminated ‘omega-carbamoyloxy urethane’ moiety/block based binder.

2. A binder as claimed in claim 1 wherein said at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block includes urea terminated poly (beta and/or gamma and/ or delta and/or omega-carbamoyloxy urethane) and includes one or more
copolymers of poly(beta-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(beta-hydroxycarbamate) and poly (omega-carbamoyloxy urethane); urea terminated poly (omega-carbamoyloxy urethane) and poly (omega-carbamoyloxy urethane);
copolymers of poly(omega-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(omega-hydroxycarbamate) and poly (omega-carbamoyloxy urethane); urea terminated poly(omega-carbamoyloxy urethane) and poly (omega-carbamoyloxy urethane).

3. A binder as claimed in anyone of claims 1 or 2 comprises blends of one or more poly(beta-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(beta-hydroxycarbamate) and poly(omega-carbamoyloxy urethane); urea terminated poly(omega-carbamoyloxy urethane) and poly(omega-carbamoyloxy urethane);
poly(omega-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(omega-hydroxycarbamate) and poly(omega-carbamoyloxy urethane); urea terminated poly(omega-carbamoyloxy urethane) and poly(omega-carbamoyloxy urethane).

4. A binder as claimed in anyone of claims 1-3 wherein said binder comprising at least one urea terminated poly (omega-carbamoyloxy urethane)moiety/ block includes urea terminated poly (beta/omega-carbamoyloxy urethane) which is a reaction product of: an amine-functionalized poly(beta/omega-hydroxycarbamate) of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and-OH value ranging from 30 to 300 mg KOH/gm, and urea,
resulting from the reaction of plurality of reactive secondary hydroxyl groups of omega/beta-hydroxy carbamate repeat units borne on a polymeric HNIPU backbone with urea and generating further pendant carbamate functionalities pendant from and adjacent to said carbamate repeat unit based polymeric HNIPU backbone and providing for said urea terminated poly(omega-carbamoyloxy urethane).

5. A binder as claimed in anyone of claims 1-4 wherein said binder comprising at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety is a reaction product of an amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW (amine hydrogen equivalent weight) and selective –OH value, and urea, and
also includes adducts resulting from reaction of amine terminals of said amine-functionalized poly(beta/omega-hydroxycarbamate) representing select AHEW (amine hydrogen equivalent weight) with urea thereby favouring urea terminated poly(omega-carbamoyloxy urethane).

6. A binder as claimed in anyone of claims 1-5 including binder derivatives comprising additional polyol and polyamine functionality derivatized at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety based binder, selectively derivatized with one or more alcohol/s, glycol/s, amine/s, polyamine/s favouring co-polycarbonate urethane, polyurea urethane moieties on said binder and/ or blends of binders thereof.

7. A binder as claimed in claim 4 wherein said pendant carbamate functionalities pendant from said polymeric beta/omega-hydroxy carbamate repeat units borne HNIPU backbone post reaction with urea and remaining urea unreacted beta/omega-hydroxy carbamates on said HNIPU backbone are both adapted for curing with crosslinker/s including polyaldehye and/or mixtures thereof selectively yielding additional bis-carbamate (or geminal urethanes) to thereby generate coats/ thermoset compositions with closely disposed urethane linkages in branched fashion having improved drying, sandability and hardness performance of said coat attained in short period of time preferably within 15 min-4 hrs.

8. A binder as claimed in anyone of claims 1-7 wherein said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW and selective –OH value is blended with at least one OH-rich binder selected from polyester, polyacrylic, polycarbonate and alkyd and co-reacted with urea.

9. A binder as claimed in anyone of claims 1-8 comprising said at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety as a reaction product of said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW and selective –OH value with urea, blended with at least one reaction product of said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd and urea.

10. A binder as claimed in anyone of claims 1-9 wherein said polyacrylic resin is obtained of MMA, BA, Styrene and HEMA wherein the hydroxyl group of HEMA is converted to carbamate.

11. A binder as claimed in anyone of claims 1-10 wherein said binder including at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety is adapted for curing with at least one or more cross-linker including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof to provide for thermoset curing/coating formulations/films thereof.

12. A binder as claimed in anyone of claims 1-11 wherein said binder derivatives comprising said additional polyol and polyamine functionality derivatized at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety based binder is adapted for curing with at least one or more cross-linker including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof to provide for thermoset curing/coating formulations/films thereof.

13. A binder as claimed in anyone of claims 1-12 adapted for ambient temperature curing/ coating formulations thereof in combination with cross-linker including at least one polyaldehyde or mixtures thereof favoring highly branched urethane crosslinking density for rapid curing at ambient temperature.

14. A binder as claimed in anyone of claims 1-13 is either adapted for a coating comprising said at least one urea terminated poly (beta/omega-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker or mixtures thereof including regular poly(isocyanate), polyaldehydes; or
is adapted for coating formulations comprising said at least one urea terminated poly (beta/omega-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker including regular poly(isocyanate), polyaldehydes as components of a formulation favoring generation of said coating.

15. A binder as claimed in anyone of claims 1-14 is either adapted for a coating comprising said additional polyol and polyamine functionality derivatized at least one urea terminated poly (omega/beta-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker or mixtures thereof including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof; or
is adapted for coating formulations comprising said at least one urea terminated poly(omega-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof as components of a formulation favoring generation of said coating.

16. A binder as claimed in anyone of claims 1-15 adapted for curing/ coating formulations thereof comprising at least one urea terminated poly (omega/beta-carbamoyloxy urethane) moiety based binder or derivatives thereof as a reaction product of said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW and selective –OH value with urea; blended with
at least one reaction product of said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd and urea; and
further co-cured with at least one or more cross-linker including polyaldehyde or mixtures thereof favouring ambient temperature thermoset curing/coating formulations/films thereof.

17. A binder as claimed in anyone of claims 1-16 adapted for curing/ coating formulations thereof comprising
a blend comprising said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW and selective –OH blended with said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd; reacted with urea;
further co-cured with at least one or more cross-linker including polyaldehyde favouring ambient temperature thermoset curing/coating formulations/films thereof.

18. A binder as claimed in anyone of claims 1-17 adapted for a coating or coating formulations thereof involving said resin with 30% - 40% by weight solid and said cross-linker with 20%-40% by weight solid.

19. A binder as claimed in anyone of claims 1-18 adapted for a coating or coating formulations thereof wherein said cross-linker includes polyaldehyde or mixtures thereof and are selected from dialdehyde to polyaldehydes including cyclohexyldialdehyde (CHDA), PARALOID™ EDGE XL-195 (DOW).

20. A binder as claimed in anyone of claims 1-19 adapted for a coating or coating formulations thereof providing thermoset curing/coating films wherein the touch dried film formed only after 15 min and has gloss of 65 to 94 gloss unit measured at 60°.

21. A binder as claimed in anyone of claims 1-20 adapted for a coating or coating 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.

22. A binder as claimed in anyone of claims 1-21 adapted for a coating or coating formulations thereof wherein said aromatic content is chemically connected with HNIPU backbone based 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.

23. A binder as claimed in anyone of claims 1-22 wherein said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW (amine hydrogen equivalent weight) and select –OH value is a reaction product of a poly(cycloalkylene carbonate) and polyamine including amine 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.

24. A binder as claimed in claim 23 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-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).

25. A binder as claimed in claim 23 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.

26. A binder as claimed in claim 23 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-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.

27. A binder as claimed in anyone of claims 1-26 adapted for a coating or coating formulations thereof as clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

28. Process for preparation of binder as claimed in anyone claims 1-27 comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block including urea terminated poly (beta and/or gamma and/ or delta and/or omega-carbamoyloxy urethane) involving the steps of:
providing precursor HNIPU resin of amine-functionalized poly(beta/omega-hydroxycarbamate) of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and having hydroxyl functional groups with-OH value ranging from 30 to 300 mg KOH/gm for reaction with urea to result in said binder comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block as represented hereunder

wherein: m=2, 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
wherein in said binder the pendant carbamate pendant from and adjacent to urethane repeat unit of said HNIPU backbone is a result of urea reacted secondary hydroxyl groups sourced of said omega(?)-hydroxycarbamate repeat units on said HNIPU backbone favouring at least one urea terminated ‘omega-carbamoyloxy urethane’ moiety/block based binder.

29. Process for preparation of said binder as claimed in claim 28
obtained as a reaction product by reacting an amine-functionalized poly(omega/ beta-hydroxycarbamate) having polymeric HNIPU backbone of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and with-OH value ranging from 30 to 300 mg KOH/gm with urea, whereby plurality of reactive secondary hydroxyl groups of omega/ beta-hydroxy carbamate repeat units borne on said polymeric HNIPU backbone reacts with urea to thus generate further pendant carbamate functionalities pendant from and adjacent to said carbamate repeat unit based polymeric HNIPU backbone thereby yielding biscarbamate/ carbamoyloxy-urethane comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block.

30. Process for the preparation of binder as claimed in anyone of claims 28 or 29 wherein amine terminals of said amine-functionalized poly(omega/beta-hydroxycarbamate) representing selective AHEW (amine hydrogen equivalent weight) also reacts with urea providing for related adducts including said urea terminated poly(omega-carbamoyloxy urethane) moiety based binder.

31. Process for the preparation of binder as claimed in anyone of claims 28-30 wherein said generated urea terminated poly(omega/beta-carbamoyloxy urethane) moiety based binder is further derivatized with additional polyol and polyamine functionalities including selective derivatization with one or more alcohol/s, glycol/s, amine/s, polyamine/s to yield co-polycarbonate urethane, polyurea urethane moieties on said binder and/ or blends of binders thereof.

32. Process for preparation of binder as claimed in anyone of claims 28-31 wherein said amine-functionalized poly(omega/beta-hydroxycarbamate) of AHEW in the range of 400 to 5000 and having selective –OH value in the range of 30 to 300 mg KOH/gm is blended with at least one OH-rich binder selected from polyester, polyacrylic, polycarbonate and alkyd prior to co-reaction with urea;
such that other OH-rich binder/s are added at the tail-end of the reaction between said amine-functionalized poly(omega/beta-hydroxycarbamate) of AHEW in the range of 400 to 5000 with the urea.

33. Process for preparation of binder as claimed in anyone of claims 28-32 wherein said at least one urea terminated poly(omega/beta-carbamoyloxy urethane) moiety based binder as a reaction product of said amine-functionalized poly(omega/beta-hydroxycarbamate) or derivatives thereof, and urea, is blended with
at least one reaction product of said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd and urea.

34. Process for preparation of binder as claimed in anyone of claims 28-33 wherein said polyacrylic resin is obtained by reacting MMA, BA, Styrene and HEMA and wherein the hydroxyl group of HEMA is converted to carbamate by reaction with urea.

35. Process for preparation of binder as claimed in anyone of claims 28-34 wherein generation of additional carbamate functionalities adjacent to and pendant from said polymeric HNIPU backbone takes place in presence of catalyst preferably zinc acetate catalyst.

36. Process for preparation of binder as claimed in anyone claims 28-35 wherein providing said precursor HNIPU resin of amine-functionalized poly(omega/beta-hydroxycarbamate) of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 is obtained from the reaction of a poly(cycloalkylene carbonate) and polyamine including reaction of amine and/or imine withpolycyclic carbonate and/or cyclic carbonate based (HNIPU) binder, said polycyclic carbonate and/or cyclic carbonate is obtained from the reaction 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.

37. Process for preparation of binder as claimed in anyone of claims 28-36 and coating or coating formulations thereof wherein said at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block based binder including urea terminated poly poly(omega and/or delta and/or gamma and/ or beta-carbamoyloxy urethane) moiety based binder thus generated is subsequently cured/cross-linked with cross-linker including polyaldehye or mixture thereof to yield additional bis-carbamate (or geminal urethanes) as coats/ thermoset compositions with closely disposed urethane linkages in branched fashion having improved drying, sandability and hardness performance of said coat attained in short period of time preferably within 15 min-4 hrs preferably at ambient temperatures.

38. Process for preparation of binder as claimed in claim 37 and coating or coating formulations thereof wherein said cross-linkers includes polyisocyanates, polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof to provide for thermoset curing/coating formulations/films thereof.

39. Process for preparation of binder as claimed in anyone of claims 28-38 and coating or coating formulations thereof wherein said curing with crosslinkers preferably polyaldehye or mixtures thereof is done in the presence of acid catalyst including aromatic sulfonic acids selected from and including p-toluenesulfonic acid (PTSA), naphthalene disulphonic acid, 2-methyl naphthalene disulphonic acid preferably p-toluenesulfonic acid (PTSA) enabling ambient temperature curing.

Dated this the 29th day of August, 2018 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
IN/PA-199
, Description:FIELD OF INVENTION

The present invention provides for a binder with hydroxyl non-isocyanate polyurethane (HNIPU) backbone comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block adapted for curing with at least one or more cross-linker including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof to provide for thermoset curing/coating formulations/films thereof. The present invention generally relates to crosslinked polyurethanes with high concentrations of very closely disposed urethane linkages obtained from isocyanate-free (HNIPU) backbone and substantially isocyanate-free multicomponent compositions, processes and other related inventions.

BACKGROUND ART

Crosslinked isocyanate polyurethanes and multicomponent systems thereof according to REACH, involve PU that are identified as carcinogen, mutagen and toxic for reproduction, thus research and development efforts on non-isocyanate polyurethane (NIPU) synthesis and their room temperature curable chemistries has identified most promising material science as well as the paints and coating industry. In the paints and coating industry its application is visualized either as a base (i.e. binder or paint, to be curable by a hardener) or as a hardener (to cure a base), to finally provide a thermoset coating film. In regular polyurethane coating, where the urethane linkage is formed by curing a mixture of suitable polyol with polyisocyanate as hardener via step-growth polymerization mechanism.Investigations of NIPU synthesis are mostly concerned with the reaction of a poly-functional cyclic carbonate with a polyfunctional amine into a single phase thermoplastic or a cross-linked thermosets. These isocyanate free polyurethane developed in the prior art have drawbacks, such as, NIPU must be cured at a curing temperature above 80 °C to achieve effective cross-linked polyurethane. This high temperature curing prevent them being used in floor, furniture, automotive coatings. Further, the synthesized thermoplastic NIPU polymer has a considerable hydroxyl concentration that may be responsible for tackiness and slow drying and non sandable coating in wood finish applications.

On this reference is drawn to Poussard, L et al. in Macromolecules, 2016, 49, pp 2162–2171disclosing elastomeric NIPUs derived from oligoamides and CSBO exhibited a better rigidity, an improved elongation at break (erup to 400%), and a higher thermal stability (T95 wt % > 350 °C) than those of starting oligoamides.

US2011/0313091 A1, discloses the ambient temperature curable isocyanate free composition containing polycarbamate and aldehyde cross linker and acid catalyst.

US 7,442,325 B2, discloses aminoplast-based crosslinking compositions and their method of preparation. The compositions are useful as crosslinking agents in curable compositions that contain materials or polymers having active hydrogen groups.

US 6,541,594 B2, discloses coating compositions comprising a reactive component (a) which is substantially free of any heteroatoms and is not a crystalline solid at room temperature and which comprises from (i) 12 to 72 carbon atoms, and at least two functional groups (ii), and (b) a crosslinking agent comprising a plurality of functional groups (iii) reactive with the functional groups (ii) of compound (a), wherein functional groups (ii) and (iii) are selected such that reaction there between produces a thermally irreversible chemical linkage.

US 5,356,669; and US 6,541,594 B2. U.S. Patent Number 5,356,669 discloses polyurethanes based on reaction products of (a) a first component comprising a polymer backbone having appended thereto at least one carbamate group, and (b) a second component comprising a compound having a pluralityof groups that are reactive with said carbamate group.

EP 2397506 A1,discloses the curable isocyanate-free compositions for preparing crosslinked polyurethane.

deRuiter, B., et al in Progress in Organic Coatings, 2006,55, pp.154-159 teaches coating formed through metal-ligand supramolecular interaction. Theprocessreferstothecombination of a covalent cationic crosslinkingstepandasupramolecular,reversiblecross-linkingstep(throughmetal–ligand interaction). This could lead to a novel class of coatings with unprecedented rheological properties, with potential applications as“self-healing” coatings.

Montaranl,D et al. in Journal of Polymer Science: Part A: Polymer Chemistry,2010, 48, pp1133-1141 teaches to combine the supramolecular chemistry of heterocyclic ureas with the chemistry of epoxides to synthesize new crosslinked materials incorporating both chemical and supramolecular hydrogen-bonded links.

Han,J.T., et al in J. AM. CHEM. SOC. 2004, 126, pp4796-4797 discloses a novel method to fabricate a superhydrophobic surface by the simple sol-gel process at room temperature using a supramolecular organosilane having quadruple hydrogen bonds.

Schubert, U. S. El-ghayoury, A., et al. in E-Polymers, 2003, 053, pp 1-13 relate to terpolymers based on poly(methyl methacrylate), containing terpyridinemoieties as well as epoxide groups, that were synthesized via free-radical polymerization. The products were cross-linked non-covalently with iron(II) ions and covalently by treatment with AlCl3

Liu,R., et al. in Progress in Organic Coatings, 2016, 101, pp 122-129 teaches a novel UV-curable self-healing oligomer designed on the basis of a quadrupolar hydrogen bond system. The oligomer is formed by reacting a mixture of a hydrogen bonding group and a photosensitive monomer with three-arm polyols.

US20160230035, describes floor coating compositions containing supramolecular polymers.

US8653174B2, by Dow Global Technologies LLC,provides a multi-component composition that is substantially isocyanate-free and comprises a polycarbamate as a first component and a polyaldehyde or an acetal or hemiacetal thereof as a second component and further comprises an effective amount of a triggering agent such that the first and second components to cure at a temperature of from 0?C to less than 80?C to form a crosslinked polyurethane. The multi-component composition forms an ambient temperature curable composition when all of its components are combined that has a pH of 7.0 or less. The polycarbamate is, for example, the condensation product of one or more polyols with an unsubstituted carbamic acid alkyl ester or urea wherein suitable polyols may include, for example, an acrylic, saturated polyester, alkyd, polyether or polycarbonate polyol.
Typically the polycarbamate of this prior art is prepared by (a) reacting a polyol with O-methyl carbamate or urea to give the polycarbamate; (b) reacting a polyisocyanate with an O-hydroxy(C2-C2O)alkyl-carbamate to give the polycarbamate; or (c) reacting the O-hydroxy(C2-C2O) alkyl-carbamate with methacrylic anhydride to give a 2-carbamoylalkyl methacrylate, and then polymerizing the 2-carbamoylalkyl methacrylate with an acrylic acid monomer to give the polycarbamate as a polyacrylic-based polycarbamate.
The polyaldehyde of the second component of this prior art may have two aldehyde groups (also referred to herein as a dialdehyde), wherein at least one of the two aldehyde groups reacts with two carbamate groups from the same polyurethane chain (molecule) so as to form the crosslinked polyurethane comprising a plurality of geminalbis(urethane) groups. The two aldehyde groups of the dialdehyde may react With two carbamate groups from two different polyurethane chains so as to form the crosslinked polyurethane comprising a plurality of germinal bis(urethane) groups. Suitable polyaldehydes of the present invention have two, three, four or more aldehyde groups. A polyaldehyde having three aldehyde groups is also referred to herein as a trialdehyde.
However, this prior art does not disclose that the base polyol itself can be a NIPU obtained by reaction of a poly(cyclic carbonate) and a polyamine which in substantially containing high proportion (up to 100%) secondary alcohols is difficult to react with urea as compared to other known polyols based on acrylic, polyester or alkyd backbones having predominantly primary alcohols.

US 20020107325 by BASF Corp. is directed to clearcoat coating composition contains (a) a first vinyl copolymer; (b) a second vinyl copolymer having hydroxyl functionality, preferably primary hydroxyl functionality; and (c) a curing agent component including at least an aminoplast curing agent and optionally a blocked polyisocyanate curing agent. The first vinyl copolymer is prepared from 35 wt.% of nonfunctional monomers containing carbamate functionality and hydroxyl functionality, wherein at least part of the hydroxyl functionality is on monomer units including an optionally branched alkyl group having at least about six carbon atoms.Thus, a clear coat composition for vehicles comprises a carbamate-modified hydroxyethyl methacrylate glycidylneodecanoate-acrylic acid adduct copolymer, cyclohexyl methacrylate-2-ethylhexyl acrylate-2-ethylhexyl methacrylatehydroxyethyl acrylates copolymer, Cymel 323, dimethylpyrazole blocked isocyanurate of hexamethylenediisocyanate, and dodecyl-benzene sulfonic acid. Types of clearcoat coating composition comprising a carbamate-functional or urea-functional material comprising at least two functional groups, at least one of which is a carbamate or urea group that is the reaction product of(1) an hydroxyl group of a first compound that is the result of a ring-opening reaction between a compound with an epoxy group and a compound with an organic acid group and(2) cyanic acid or a carbamate or urea group-containing compound. The curing agent for such clear coating compositions are taught to be aminoplast curing agent and optionally a polyisocyanate curing agent. Aminoplastcrosslinkersare directed to have active methylol or methylalkoxygroups. Examples of preferred aminoplast curing agent compounds include melamine formaldehyde crosslinkers, including monomeric or polymeric melamine resin and partially or fully alkylated melamine resin, urea resins, and methylolureas such as urea formaldehyde resin, alkoxyureas such as butylated urea formaldehyde resin. The clearcoat composition further includes a polyisocyanate curing agent, which preferably is blocked.
While the above prior art teaches reaction between secondary hydroxyl group (generated from epoxy ring opening) and urea to produce carbamate functionality the curing is still only with aminoplast resin meaning melamine-formaldehyde, urea-formaldehyde etc., along with optionally polyisocyanate curing agents.

WO 1999035198 A1 by BASF Corporation provides a curable coating composition comprising (a) a first component comprising at least two functional groups, at least one of which is a carbamate or urea group that is the reaction product of: (1) a hydroxyl group that is the result of a ring-opening reaction between an epoxy group and an organic acid group, and (2) cyanic acid or a carbamate or urea group;
(b) a curing agent having a plurality of functional groups that are reactive with component (a), and (c) a second component having functional groups that are reactive with component (a) or component (b) or both components (a) and (b).
Further a curable coating composition is also recited wherein component (c) comprises a carbamate-functional material that is the reaction product of (1) a first material that is the reaction product of a mixture including(A) a polyisocyanate and(B) an active hydrogen-containing chain extension agent with(2) a compound comprising a group that is reactive with said first material and a carbamate group or group that can be converted to carbamate.
It is further suggested therein that groups that can be converted to carbamate include cyclic carbonate groups, epoxy groups, and unsaturated bonds. Cyclic carbonate groups can be converted to carbamate groups by reaction with ammonia or a primary amine, which ring-opens the cyclic carbonate to form a ß-hydroxy carbamate. Epoxy groups can be converted to carbamate groups by first converting to a cyclic carbonate group by reaction with C02.Further to the above a higher curing temperature is suggested that vary depending on the particular blocking groups used in the cross-linking agents, however they generally range between 93 °C and 177 °C.
While this prior art suggests carbamate formation either with a secondary hydroxyl originating from the ring opening of a glycidyl function (epoxy) or transesterification of amine with cyclic carbonates to provide the beta-hydroxy carbamates, does not teach any base NIPU material comprising a plurality of aforementioned beta-hydroxy carbamate borne on a polymeric backbone that is further converted into pendant carbamate functionalities followed by curing with polyaldehyde. Also this prior art does not teach any ambient temperature curing but curing only at elevated temperatures.

WO 2000026313 by BASF Corporation is directed to a curable coating composition that includes at least three components. The coating composition includes a component (a) having at least one carbamate group or urea group and having a lactone or hydroxy carboxylic acid moiety. The second component (b) of the coating composition is one or more of three materials. First, the second component can be a polymer resin (b)(1) comprising active hydrogen-containing functional groups reactive with the third component (c). Secondly, the second component can be a compound (b)(2) having at least one carbamate group or terminal urea group according to the invention and having at least two linking groups that are urethane or urea. Finally, the second component can be a compound (b)(3) having at least two groups selected from carbamate groups, terminal urea groups, or combinations of the two and at least four urethane or urea linking groups. The third component of the coating composition is a curing agent that is reactive with the first two components. Preparation of coated articles using the compositions of the invention is also disclosed. One preferred example of such a compound under (a) (1) has a carbamate group and a hydroxyl group. One preferred example of such a compound is a hydroxyalkyl carbamate, particularly a ß-hydroxyalkyl carbamate. In a preferred embodiment, the cure temperature is preferably between 115°C and 150°C, and more preferably at temperatures between 115°C and 140°C for a blocked acid catalyzed system. For an unblocked acid catalyzed system, the cure temperature is preferably between 80°C and 100°C. Hence predominantly a beta-hydrogen carbamate resin is disclosed that reacts with a curing agent at an elevated temperature and does not recite any further carbamate derivatization of beta-hydroxyl group of the beta-hydroxy carbamate at ambient temperature particularly with polyaldehyde curing agents.

While the curing of HNIPU (hydroxyl non-isocyanate polyurethane) can be done with epoxy rich acrylic resin or alkyd resin under ambient condition. In another way the curing of HNIPU can be done using polyaldehyde like glyoxal, CHADA (1,4-cyclohexanedicarboxyaldehyde) through imine formation at ambient temperature. Other way the curing of NIPU can also be possible through urea-formaldehyde or amino resin curing route. In another way the curing of NIPU can be done through isocyante route at room temperature or through ester formation at elevated temperature. All these routes are not preferred due to durability or colour issue.

It is thus the need of the day to avoid all these undesired routes of crosslinking of hydroxyl non-isocyanate polyurethane (HNIPU) to provide a thermoset coating film and to seek to solve the problem of providing substantially isocyanate-free composition that would also be ambient temperature curable and would give cross-linked polyurethane having high concentrations of very closely disposed urethane linkages and would also favour higher levels of cross-linking to improve the drying, sandability and hardness performance to find end use and application in diverse paint applications including wood finish or industrial applications.

OBJECTS OF THE INVENTION

It is thus a primary object of the present invention to provide for total polyurethane formulations/coating comprising select binder with hydroxyl non-isocyanate polyurethane(isocyanate free-HNIPU) backbone that would provide for high concentrations of very closely disposed urethane linkages crosslinked/cured with crosslinkers including polyaldehyde that would preferably crosslink at ambient temperatures to provide for improved drying, sandability and hardness performance of the coating is short period of time preferably within 3-4 hrs.

It is another object of the present invention to provide for said formulations/coating comprising select binder with hydroxyl non-isocyanate (isocyanate free) polyurethane HNIPU backbone that would allow addition of mass to HNIPU binder upon carbamate formation with inexpensive urea to contribute increase in solids and reduction in cost of the HNIPU binderand would be further crosslinked/cured with crosslinkers including polyaldehyde.

It is yet another object of the present invention to provide for said formulations/coating comprising select binder with hydroxyl non-isocyanate (isocyanate free) polyurethane HNIPU backbone that would enable carbamate derivatization of the multiplicity of hydroxyl group to aid associative tendency thereby enhancing the solubility of the binder and its viscosity stabilization by using protic solvent and would further be crosslinked/cured with crosslinkers including polyaldehyde.

It is still another object of the present invention to provide for said formulations/coating comprising said select binder with hydroxyl non-isocyanate (isocyanate free) polyurethane HNIPU backbone which due to the carbamate derivatization of HNIPU followed by crosslinking/ curing with crosslinkers including polyaldehyde would aid in avoiding the colour intensification due to conversion of terminal amines into amide and urea successably vis-à-vis conventional immine functionality generation upon cross-linking of amine terminated HNIPU with same polyaldehyde leading to unwanted intensification of colour of the binder in the yellow to red zone.

SUMMARY OF THE INVENTION
Thus according to the basic aspect of the present invention there is provided a binder with hydroxyl non-isocyanate polyurethane (HNIPU) backbone comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block represented by the following structure

wherein: m=2,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
wherein in said binder the pendant carbamate pendant from and adjacent to urethane repeat unit of said HNIPU backbone is a result of urea reacted secondary hydroxyl groups sourced of said omega(?)-hydroxycarbamate repeat units on said HNIPU backbone favouring at least one urea terminated ‘omega-carbamoyloxy urethane’ moiety/block based binder.

Thus in the above binder the pendant carbamate as seen in the above structure, considered as second carbamate being pendant from and adjacent to carbamate repeat units of said HNIPU backbone considered as first carbamate sourcing secondary hydroxyl group upon reaction with urea results in at least one urea terminated ‘bis-carbamate’ moiety/ block based binder, or more appropriately termed as at least one urea terminated ‘omega-carbamoyloxy urethane’ moiety/block based binder.

The terminology ‘bis-carbamate’ as and where used for the purposes of the present invention should be understood to result from carbamate in the pendant or a terminal that is a true carbamate, whereas the carbamate occurring on the backbone as repeat unit is called urethane as per conventional nomenclature protocol. Therefore as per the generic structure of the binder provided above the present invention provides for significantly special carbamoyloxy-urethane, where one carbamate is connected by its oxygen to another urethane.

Further in case of x>0 of (CH2)x, the -OH of the hydroxyurethane does not remain beta (ß) anymore but becomes gamma, delta etc. in terms of positioning wherein in generic nomenclature it is referred to as omega (such as in omega-hydroxy fatty acids). Therefore, for the present invention the binder may also comprise of some free omega-hydroxycarbamate moieties unreacted with urea also including free gamma/ delta-hydroxycarbamates unreacted with urea.

Preferably, said binder comprises at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block includes urea terminated poly (beta and/or gamma and/ or delta and/or omega-carbamoyloxy urethane); and includes one or more
copolymers of poly(beta-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(beta-hydroxycarbamate) and poly (omega-carbamoyloxy urethane); urea terminated poly(omega-carbamoyloxy urethane) and poly (omega-carbamoyloxy urethane);
copolymers of poly(omega-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(omega-hydroxycarbamate) and poly (omega-carbamoyloxy urethane); urea terminated poly(omega-carbamoyloxy urethane) and poly (omega-carbamoyloxy urethane).

More preferably said binder comprises binder blends of one or more
poly(beta-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(beta-hydroxycarbamate) and poly(omega-carbamoyloxy urethane); urea terminated poly(omega-carbamoyloxy urethane) and poly(omega-carbamoyloxy urethane);
poly(omega-hydroxycarbamate) and urea terminated poly(omega-carbamoyloxy urethane); poly(omega-hydroxycarbamate) and poly(omega-carbamoyloxy urethane); urea terminated poly(omega-carbamoyloxy urethane) and poly(omega-carbamoyloxy urethane).

According to another preferred aspect of the present invention there is provided said binder wherein said binder comprising at least one urea terminated poly (omega-carbamoyloxy urethane)moiety/ block includes urea terminated poly (beta/omega-carbamoyloxy urethane) which is a reaction product of: an amine-functionalized poly(beta/omega-hydroxycarbamate) of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and-OH value ranging from 30 to 300 mg KOH/gm, and urea,
resulting from the reaction of plurality of reactive secondary hydroxyl groups of beta/omega-hydroxy carbamate repeat units borne on a polymeric HNIPU backbone with urea and generating further pendant carbamate functionalities pendant from and adjacent to said carbamate repeat unit based polymeric HNIPU backbone and providing for said urea terminated poly(omega-carbamoyloxy urethane).

It is thus surprisingly found by way of the present invention that said binder with HNIPU backbone comprising at least one urea terminated poly (omega-carbamoyloxy urethane) moiety/ block and formulations/coating comprising the same when crosslinked/ cured with at least one crosslinker including polyaldehyde could generate coats/ thermoset compositions with closely disposed urethane linkages in branched fashion having improved drying, sandability and hardness performance of said coat attained preferably in short period of time preferably within 15 min-4 hrs.

Said binder could be achieved when said HNIPU backbone having plurality of secondary hydroxyl group based beta and/or omega-hydroxy carbamate repeat units borne on said polymeric HNIPU backbone, considered as first carbamate backbone, which is also amine-functionalized poly(beta/omega-hydroxycarbamate) of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and-OH value ranging from 30 to 300 mg KOH/gm, further generates pendant carbamate functionalities upon reaction with urea wherein the pendant carbamate functionality thus generated being the second carbamate functionality is pendant from and adjacent to first carbamate of said polymeric HNIPU backbone thereby resulting in ‘bis-carbamate’ repeat units or more appropriately ‘omega-carbamoyloxy urethane’ adapted for further crosslinking by including polyaldehye and/or mixtures thereof selectively further yielding bis-carbamate (or geminal urethanes) therefore generating said coats/ thermoset compositions with closely disposed urethane linkages in branched fashion having improved drying, sandability and hardness performance of said coat attained in short period of time preferably within 15 min-4 hrs.

Hence the special inventive binder of the present invention is qualified based on the fact that the secondary hydroxyl groups of the beta/omega-hydroxycarbamate repeat unit based HNIPU backbone, itself is getting converted to another pendant carbamate which is the second carbamate. So this second carbamate is pendant from the first carbamate repeat unit based HNIPU backbone itself, hence ‘bis-carbamate’ repeat unit gets formed more appropriately ‘omega-carbamoyloxy urethane’ getting formed .

Said omega/beta-hydroxy carbamate functions borne on a polymeric HNIPU backbone on reacting with urea generates further carbamate functions, thereby creating two immediately adjacent carbamate functions separated only by two (02/03/04) carbon atoms, wherein one carbamate (first carbamate) is on the HNIPU polymer backbone, which said polymer backbone is an oil derived or epoxy derived or carbonate derived HNIPU urethane polymer, and the other (second) carbamate that is generated is pendant from the HNIPU backbone and adjacent to the first carbamate resulting in ‘bis-carbamate’ or more appropriately ‘omega-carbamoyloxy urethane’ wherein the pendant carbamate of said ‘bis-carbamate’/ ‘omega-carbamoyloxy urethane’ is further cured by crosslinkers including polyaldehyde to preferably generate further bis-carbamate (or geminal urethanes), thereby generating a high concentration of very closely disposed urethane linkages, favouring improved drying, sandability and hardness performance of the coating in a short period of time preferably within 3-4 hrs.
In the formulation/ coating of the present invention, the preferable ambient temperature curing happened via the formation of an additional urethane linkage originating from the carbamate pendant from the HNIPU polymer backbone thereby delivering a totally polyurethane coating composition.

Hence hydroxyl non-isocyanate polyurethane HNIPU backbone, which HNIPU not only has the beta/omega-hydroxycarbamate repeat units but also has amine terminals (represented by the range of AHEW or the Amine hydrogen equivalent wt.) and both such functional groups upon reaction with urea, not only results in carbamates/omega-carbamoyloxy moieties pendant from the HNIPU backbone but also results in adducts resulting from reaction of said amine terminals preferably of HNIPU backbone with urea thereby favouring urea terminated poly(omega-carbamoyloxy urethane) that also contributes to the mechanical properties of the coating.

Hence urea is allowed to perform ureolysis or aminolysis reaction on the existing beta/omega-hydroxycarbamate repeat units of the HNIPU polymer backbone thereby dropping viscosity and MW of the polymers and also resulting into generation of newly opened OH groups (which would show up as low consumption of OH value) in spite of urea getting consumed, based on select reaction conditions time of reaction, temperature and pressure revealing the select reaction conditions that causes viscosity builds or drops respectively and also the OH value shows as consumed or not consumed respectively.

Therefore industrial utility based on high urethane crosslinking density is achieved in a branched fashion resulting in fast curing, surface dry and sandability (5 hours or less) and also overnight hardness buildup surprisingly in spite of having large oil backbone in the resultant coating that still maintains high gloss and wet look, contraposed to the general notion that the oils based backbones provides high gloss and wet look upon slow drying and the fast drying characteristics being generally known to take away the gloss building capability of oil based alkyds resulting into relatively mat surface finish.

It is thus a significant finding of the present invention that said binder with hydroxyl non-isocyanate polyurethane(HNIPU) backbone comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block and curing formulations/coating comprising the same could be provided which when crosslinked with crosslinkers including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof and when preferably crosslinked with polyaldehydes preferably cures at ambient temperatures, which said binder due to the carbamate derivatization of HNIPU backbone followed by polyaldehyde curing aids in avoiding the colour intensification due to conversion of terminal amines into amide and urea successably vis-à-vis conventional immine functionality generation upon cross-linking of amine terminated HNIPU with same polyaldehyde that leads to intensification of colour of the binder in the yellow to red zone.

Preferably said binder of the present invention comprising at least one at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety is a reaction product of an amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW (amine hydrogen equivalent weight) and selective –OH value, and urea, and
also includes adducts resulting from reaction of amine terminals of said amine-functionalized poly(beta/omega-hydroxycarbamate) representing select AHEW (amine hydrogen equivalent weight) with urea thereby favouring urea terminated poly(omega-carbamoyloxy urethane).

More preferably said binder includes binder derivatives comprising additional polyol and polyamine functionality derivatized at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety based binder, selectively derivatized with one or more alcohol/s, glycol/s, amine/s, polyamine/s favouring co-polycarbonate urethane, polyurea urethane moieties on said binder and/ or blends of binders thereof.

Preferably in said binder wherein said pendant carbamate functionalities pendant from said polymeric beta/omega-hydroxy carbamate repeat units borne HNIPU backbone post reaction with urea and remaining urea unreacted beta/omega-hydroxy carbamates on said HNIPU backbone are both adapted for curing with crosslinker/s including polyaldehye and/or mixtures thereof selectively yielding additional bis-carbamate (or geminal urethanes) to thereby generate coats/ thermoset compositions with closely disposed urethane linkages in branched fashion having improved drying, sandability and hardness performance of said coat attained in short period of time preferably within 15 min-4 hrs.

More preferably, in said binder said amine-functionalized poly (beta/omega-hydroxycarbamate) of selective AHEW and selective –OH value is blended with at least one OH-rich binder selected from polyester, polyacrylic, polycarbonate and alkyd and co-reacted with urea.

Further to the above a binder is provided comprising said at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety as a reaction product of said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW and selective –OH value with urea, blended with at least one reaction product of said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd and urea.

In aforesid binder said wherein said polyacrylic resin is obtained of MMA, BA, Styrene and HEMA wherein the hydroxyl group of HEMA is converted to carbamate.

According to another preferred aspect of the present invention there is provided a binder wherein said binder including at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety is adapted for curing with at least one or more cross-linker including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof to provide for thermoset curing/coating formulations/films thereof.

Preferably in said binder said binder derivatives comprising said additional polyol and polyamine functionality derivatized at least one urea terminated poly(beta/omega-carbamoyloxy urethane) moiety based binder is adapted for curing with at least one or more cross-linker including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof to provide for thermoset curing/coating formulations/films thereof.

Also preferably said binder is adapted for ambient temperature curing/ coating formulations thereof in combination with cross-linker including at least one polyaldehyde or mixtures thereof favoring highly branched urethane crosslinking density for rapid curing at ambient temperature.

Preferably said binder is either adapted for a coating comprising said at least one urea terminated poly (beta/omega-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker or mixtures thereof including regular poly(isocyanate), polyaldehydes; or
is adapted for coating formulations comprising said at least one urea terminated poly (beta/omega-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker including regular poly(isocyanate), polyaldehydes as components of a formulation favoring generation of said coating.

More preferably said binder is either adapted for a coating comprising said additional polyol and polyamine functionality derivatized at least one urea terminated poly (omega/beta-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker or mixtures thereof including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof; or
is adapted for coating formulations comprising said at least one urea terminated poly(omega-carbamoyloxy urethane) moiety based binder and at least one or more cross-linker including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof as components of a formulation favoring generation of said coating.

Preferably said binder is adapted for curing/ coating formulations thereof comprising at least one urea terminated poly (omega/beta-carbamoyloxy urethane) moiety based binder or derivatives thereof as a reaction product of said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW and selective –OH value with urea; blended with
at least one reaction product of said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd and urea; and
further co-cured with at least one or more cross-linker including polyaldehyde or mixtures thereof favouring ambient temperature thermoset curing/coating formulations/films thereof.

According to another preferred aspect said binder is provided adapted for curing/ coating formulations thereof comprising
a blend comprising said amine-functionalized poly(beta/omega-hydroxycarbamate) of selective AHEW and selective –OH blended with said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd; reacted with urea;
further co-cured with at least one or more cross-linker including polyaldehyde favouring ambient temperature thermoset curing/coating formulations/films thereof.

Preferably said binder is adapted for a coating or coating formulations thereof involving said resin with 30% - 40% by weight solid and said cross-linker with 20%-40% by weight solid.

More preferably said binder is adapted for a coating or coating formulations thereof wherein said cross-linker includes polyaldehyde or mixtures thereof and are selected from dialdehyde to polyaldehydes including cyclohexyldialdehyde (CHDA),PARALOID™ EDGE XL-195 (DOW).

Advantageously, said binderis adapted for a coating or coating formulations thereof providing thermoset curing/coating films wherein the touch dried film formed only after 15 min and has gloss of 65 to 94 gloss unit measured at 60°.

Said binder is adapted for a coating or coating formulations thereof said coating or coating formulations 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 binder is adapted for a coating or coating formulations thereof wherein said aromatic content is chemically connected with HNIPU backbone based 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.

More preferably, in said binder wherein said amine-functionalized poly (beta/omega-hydroxycarbamate) of selective AHEW (amine hydrogen equivalent weight) and select –OH value is a reaction product of a poly(cycloalkylene carbonate) and polyamine including amine 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.

Preferably in said binder 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; polyalkylenaminessuch 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 binder 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.

Preferably in saidbinder 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, 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.

Said binder is adapted for a coating or coating formulations thereof as 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 process for preparation of said binder comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block including urea terminated poly (beta and/or gamma and/ or delta and/or omega-carbamoyloxy urethane) involving the steps of:
providing precursor HNIPU resin of amine-functionalized poly(beta/omega-hydroxycarbamate) of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and having hydroxyl functional groups with-OH value ranging from 30 to 300 mg KOH/gm for reaction with urea to result in said binder comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block as represented hereunder

wherein: m=2, 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
wherein in said binder the pendant carbamate pendant from and adjacent to urethane repeat unit of said HNIPU backbone is a result of urea reacted secondary hydroxyl groups sourced of said omega(?)-hydroxycarbamate repeat units on said HNIPU backbone favouring at least one urea terminated ‘omega-carbamoyloxy urethane’ moiety/block based binder.

Preferably in said process for preparation of said binder the same is obtained as a reaction product by reacting an amine-functionalized poly(omega/ beta-hydroxycarbamate) having polymeric HNIPU backbone of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and with-OH value ranging from 30 to 300 mg KOH/gm with urea, whereby plurality of reactive secondary hydroxyl groups of omega/ beta-hydroxy carbamate repeat units borne on said polymeric HNIPU backbone reacts with urea to thus generate further pendant carbamate functionalities pendant from and adjacent to said carbamate repeat unit based polymeric HNIPU backbone thereby yielding biscarbamate/ carbamoyloxy-urethane comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block.

According to another preferred aspect of the present invention there is provided a process for the preparation of binder wherein amine terminals of said amine-functionalized poly(omega/beta-hydroxycarbamate) representing selective AHEW (amine hydrogen equivalent weight) also reacts with urea providing for related adducts including said urea terminated poly(omega-carbamoyloxy urethane) moiety based binder.

In said process for the preparation of binder said generated urea terminated poly(omega/beta-carbamoyloxy urethane) moiety based binder is further derivatized with additional polyol and polyamine functionalities including selective derivatization with one or more alcohol/s, glycol/s, amine/s, polyamine/s to yield co-polycarbonate urethane, polyurea urethane moieties on said binder and/ or blends of binders thereof.

Preferably in said process for preparation of binder wherein said amine-functionalized poly(omega/beta-hydroxycarbamate) of AHEW in the range of 400 to 5000 and having selective –OH value in the range of 30 to 300 mg KOH/gm is blended with at least one OH-rich binder selected from polyester, polyacrylic, polycarbonate and alkyd prior to co-reaction with urea;
such that other OH-rich binder/s are added at the tail-end of the reaction between said amine-functionalized poly(omega/beta-hydroxycarbamate) of AHEW in the range of 400 to 5000 with the urea.

More preferably in said process for preparation of binder said at least one urea terminated poly(omega/beta-carbamoyloxy urethane) moiety based binder as a reaction product of said amine-functionalized poly(omega/beta-hydroxycarbamate) or derivatives thereof, and urea, is blended with
at least one reaction product of said OH-rich binder selected from polyester, polyacrylic, polycarbonate, alkyd and urea.

Preferably in said process for preparation of binder said polyacrylic resin is obtained by reacting MMA, BA, Styrene and HEMA and wherein the hydroxyl group of HEMA is converted to carbamate by reaction with urea.

According to yet another preferred aspect of the process for preparation of said binder wherein generation of additional carbamate functionalities adjacent to and pendant from said polymeric HNIPU backbone takes place in presence of catalyst preferably zinc acetate catalyst.

Preferably in said process for preparation of binder wherein providing said precursor HNIPU resin of amine-functionalized poly(omega/beta-hydroxycarbamate) of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 is obtained from the reaction of a poly(cycloalkylene carbonate) and polyamine including reaction of amine and/or imine withpolycyclic carbonate and/or cyclic carbonate based (HNIPU) binder, said polycyclic carbonate and/or cyclic carbonate is obtained from the reaction 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.

Preferably in said process for preparation of binder and coating or coating formulations thereof wherein said at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block based binder including urea terminated poly poly(omega and/or delta and/or gamma and/ or beta-carbamoyloxy urethane) moiety based binder thus generated is subsequently cured/cross-linked with cross-linker including polyaldehye or mixture thereof to yield additional bis-carbamate (or geminal urethanes) as coats/ thermoset compositions with closely disposed urethane linkages in branched fashion having improved drying, sandability and hardness performance of said coat attained in short period of time preferably within 15 min-4 hrs preferably at ambient temperatures.

More preferably, in said process for preparation of binder adapted for coating or coating formulations thereof wherein said cross-linkers includes polyisocyanates, polyaldehydes, amino resin, urea formaldehyde resin or mixtures thereof to provide for thermoset curing/coating formulations/films thereof.

Preferably in said process for preparation of binder and coating or coating formulations thereof wherein said curing with crosslinkers preferably polyaldehye or mixtures thereof is done in the presence of acid catalyst including aromatic sulfonic acids selected from and including p-toluenesulfonic acid (PTSA), naphthalene disulphonic acid, 2-methyl naphthalene disulphonic acid preferably p-toluenesulfonic acid (PTSA) enabling ambient temperature curing.

DETAILED DESCRIPTION OF THE INVENTION
As discussed hereinbefore, the present invention provides for binder with hydroxyl non-isocyanate polyurethane(HNIPU) backbone comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block and curing formulations/coating comprising preferably ambient temperature curing formulations/coating comprising said binder.
Said binder comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block includes urea terminated poly (beta and/or gamma and/ or delta and/or omega-carbamoyloxy urethane) as is represented by the following structure

wherein: m=2,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
wherein in said binder the pendant carbamate pendant from and adjacent to urethane repeat unit of said HNIPU backbone is a result of urea reacted secondary hydroxyl groups sourced of said omega(?)-hydroxycarbamate repeat units on said HNIPU backbone favouring at least one urea terminated ‘omega-carbamoyloxy urethane’ moiety/block based binder.

Said curable binder/resin involving hydroxyl non-isocyanate (isocyanate free) polyurethane (HNIPU) backbone and involving plurality of reactive secondary hydroxyl groups of omega/beta-hydroxy carbamate repeat units borne on said polymeric polyurethane (HNIPU) backbone is further converted into pendant carbamate functionalities pendant from and adjacent to carbamate repeat unit in HNIPU backbone post reaction with urea, thereby providing for said biscarbamate/ carbamoyloxy-urethane and resulting in urea terminated poly poly(omega-carbamoyloxy urethane) moiety/ block based binder as a reaction product that is further cured with crosslinkers including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof preferably polyalehydes at ambient temperatures to provide for thermoset curing/coating formulations/films thereof with improved drying and sandability with desired hardness performance and gloss characteristics within a short span of time.
Examples of the present invention include the synthesis of the following that are essentially non-limiting and should not be considered to limit the scope of the present disclosure:

Examples:

First amine-functionalized generic poly(omega-hydroxycarbamate) is derived from reaction of a poly(cycloalkylene carbonate) with a polyamine according to a known protocol.
The amine-functionalized generic poly (omega-hydroxycarbamate), HNIPU, thus attained is customized to select AHEW (amine hydrogen equivalent weight) value and select -OH value and was further reacted with ureain presence of catalyst at about 130 °C to prepare the corresponding carbamate derivatives of HNIPU. It was found from several re-runs that only when AHEW (amine hydrogen equivalent weight) is in the range of 400 to 5000 and select -OH value is in the range of 30 to 300 mg KOH/gm, the same favourably reacted with urea, which in turn could be cured with desired crosslinkers including crosslinkers including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof .
Preferably said curing with said polyaldehydes results in high urethane crosslinking density achieved in a branched fashion lead to fast curing at ambient temperature, surface dry and sandability (in time 5 hours or less) and also overnight hardness buildup (surprisingly in spite of having large oil backbone in the resultant coating that still maintains high gloss and wet look, contraposed to the general notion that the oil based backbones provides high gloss and wet look upon slow drying and the fast drying characteristics being generally known to take away the gloss building capability of oil based alkyds resulting into relatively mat surface finish.

Said urea terminated poly(omega-carbamoyloxy urethane) is thus derived from reaction between an amine-functionalized poly(omega/beta-hydroxycarbamate) HNIPU of certain selective AHEW (active hydrogen equivalent weight) and –OH value with urea. Said amine-functionalized poly(omega/beta-hydroxycarbamate) in turn is derived from reaction of a poly(cycloalkylene carbonate) with a polyamine.
Said specific urea terminated poly(omega-carbamoyloxy urethane) has poly(omega-carbamoyloxy urethane) including poly(omega and/ or delta and/or gamma and/or beta-carbamoyloxy urethane) as repeat units that is hitherto before unknown.

Moreover, the poly(omega-hydroxycarbamate), which is isocyanate free HNIPU having either omega/delta/ gamma/ beta –OH group is not known in the prior art knowledge to react with either urea to result in said bis-carbamate/ carbamoyloxy-urethane, although the -OH group especially primary alcohol groups of different types of binders ranging from epoxy to polyester, alkyd and acrylics is known to react with urea and/or alkylurea.
In fact it was found that known HNIPU carbamates of any of the abovesaid binders including epoxy to polyester, alkyd and acrylics, when cured with crosslinkers including polyaldehyde, the resin takes much longer time to get the initial surface dry and initial tack-free dry to become sandable, but in comparison the urea terminated poly poly(omega-carbamoyloxy urethane) moiety based binder of the present invention dried up fast to provide initial tack-free drying and sandability within 3-4 hours without any clogging during sanding, so well that the present binder of said coating is also workable as a sanding sealer below its own top coat wherein the final hardness build-up for the topcoat is also fast enough so that it has to be moderated by adjusting catalyst concentration to maintain the gloss.

Primary alcohol based polyester, polyacrylic, polycarbonate, and alkyd (such as castor oil) while is known to react with urea to give carbamate, the present invention could employ predominantly secondary hydroxyl group based omega/beta-hydroxy carbamate repeat units borne on a polymeric HNIPU backbone and yet derivatize with urea to generate further pendant carbamate functionalities pendant from and adjacent to said carbamate repeat unit based polymeric HNIPU backbone and provide for bis-carbamate/ carbamoyloxy-urethane that could be subsequently cured with crosslinkers including aldehyde based crosslinkers.

Secondary alcohol based HNIPU sourced from vegetable oil based epoxy and further reacted with carbon dioxide, which when blended with castor oil (alkyd) has some primary alcohol groups as well, which created a balance between secondary alcohol groups and primary alcohol groups of the curing base resin blend to be derivatized into carbamate to tailor the end properties post curing.
In some cases starting from glycidyl diol and its carbonated product primary alcohol group for reaction with urea is attained which primary alcohol rich polyester, polyacrylic, polycarbonate etc. can also be blended.
Urea reacts with secondary –OH group of HNIPU and also reacts with terminal amine group of HNIPU.

It was significantly found by way of the present invention that sluggishness of the reaction of urea with secondary alcohol of HNIPU resin could be circumvented to form a carbamate derivative.
The reaction hurdle could be overcome by employing select excess of urea and performing the reaction in a certain temperature range viz.:
Either performing the reaction in the window of 140-150 °C in atmospheric pressure, or doing the reaction in temperature range of 135 °C in positive pressure of ammonia that is released from time to time from the reaction vessel enabled progress of the reaction.

At such high temperatures under such specific conditions chances of depolymerization of the HNIPU are less and reaction also proceeds moderately to completion. Separation of unreacted urea used in excess in the reaction is required, as it would tend to consume more crosslinker such as polyaldehyde as polyaldehyde also reacts with urea, and hence the cured product becomes less acid resistant, which is undesirable.
Further incorporation of some aromatic content in HNIPU derivatized with carbamate makes it less prone to alcohol abuse.
Further the excess of urea employed while reaction is selectively removed by polyalcohol thereby resulting in an industrially viable cured product when cured with crosslinkers, out of carbamate derivatization of said HNIPUbased binder of selective AHEW and –OH value.

Hence according to the principal aspect of the present invention there is provided a binder comprising urea terminated poly(omega-carbamoyloxy urethane) preferably urea terminated poly (omega and/ or delta and/ or gamma and/ or beta-carbamoyloxy urethane), wherein said urea terminated poly(omega-carbamoyloxy urethane) is a reaction product of an amine-functionalized poly(omega/beta-hydroxycarbamate) HNIPU of selective AHEW (amine hydrogen equivalent weight) and –OH value with urea.

Preferably said urea terminated poly (omega-carbamoyloxy urethane) binder has hydroxyl functional groups favouring efficient curing with crosslinkers preferably polyaldehyde preferably at ambient temperatures.

Said binder also include binder derivatives comprising additional polyol and polyamine functionality derivatized at least one urea terminated poly(omega-carbamoyloxy urethane) moiety based binder, selectively derivatized with one or more alcohol/s, glycol/s, amine/s, polyamine/s favouring co-polycarbonate urethane, polyurea urethane moieties on said binder and/ or blends of binders thereof.

More preferably said amine-functionalized poly(omega/beta-hydroxycarbamate) HNIPU precursor of selective AHEW (amine hydrogen equivalent weight) is again a reaction product of a poly(cycloalkylene carbonate) with a polyamine.

Said aforesaid amine-functionalized poly(omega/beta-hydroxycarbamate) HNIPU of selective AHEW and select –OH value is blended with at least one OH-rich binder selected from polyester, polyacrylic, polycarbonate and alkyd and co-reacted with urea, wherein said OH-rich binder is added and reacted at the tail-end of the reaction of aforesaid amine-functionalized poly(omega/beta-hydroxycarbamate) HNIPU of selective AHEW with the urea.
More preferably, a reaction product of said OH-rich binder selected from polyester, polyacrylic, polycarbonate and alkyd each reacted with urea and/ or alkylurea is blended with reaction product of aforesaid amine-functionalized poly(omega/beta-hydroxycarbamate) HNIPU of selective AHEW and select –OH value and urea.

Therefore the present invention is based on the selective binder with hydroxyl non-isocyanate polyurethane(HNIPU) backbone comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/block and preferably comprises urea terminated poly(omega and/or delta and/or gamma and/or beta-carbamoyloxy urethane) , which is a reaction product of amine-functionalized poly(omega and/or delta and/or gamma and/or beta-hydroxycarbamate) HNIPU of selective AHEW and selective –OH value, and urea resulting in said urea terminated poly(omega-carbamoyloxy urethane) adapted for curing with at least one or more crosslinkers including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof .

Said curing with said polyaldehydes resulting in high urethane crosslinking density achieved in a branched fashion lead to fast curing at ambient temperature, surface dry and sandability (in time 5 hours or less) and also overnight hardness buildup (surprisingly in spite of having large oil backbone in the resultant coating that still maintains high gloss and wet look, contraposed to the general notion that the oil based backbones provides high gloss and wet look upon slow drying and the fast drying characteristics being generally known to take away the gloss building capability of oil based alkyds resulting into relatively mat surface finish.

Thus the self-curing with polyaldehyde further generates urethane linkage at ambient temperatures.
The amine-functionalized poly (omega/delta/ gamma/ beta-hydroxycarbamate), HNIPU, of AHEW (amine hydrogen equivalent weight) in the range of 400 to 5000 and-OH value ranging from 30 to 300 mg KOH/gm was reacted with ureain presence of catalyst at 130 °C to prepare the corresponding carbamate derivatives of HNIPU. The further carbamate functionalized HNIPU resin was synthesized where the carbamate has an average of 150 or more preferably 250 and more carbamate functional groups, such as up to 400, or preferably upto 280 functional group.

Optionally HNIPU can be blended with hydroxyl rich polyester, polyacrylic, polycarbonate and alkyd and together derivatized into carbamate by urea and/or alkylurea, thereby generating a blend of carbamate NIPU and respective carbamate polymer as above.
Said above carbamate blend was cured with polyaldehyde in presence of an acid catalyst.
Preferably, the polyaldehyde is chosen from aliphatic dialdehyde or aromatic dialdehyde, more preferably cycloaliphatic dialdehyde, such as, for example 1,4-cyclohexanedicarboxyaldehyde (CHDA, cis,trans)- 1,3- cyclohexanedicarboxyaldehyde and mixtures thereof.
Aforesaid polyaldehyde curing is catalyzed by an acid with pKa of less than 6.0.

The selective binder of the present invention with hydroxyl non-isocyanate polyurethane(HNIPU) backbone comprising at least one urea terminated poly(omega-carbamoyloxy urethane) moiety/ block when cured with crosslinkers specifically polyaldehydes favoured curing at ambient temperature wherein curing happened via the formation of another urethane linkage thereby delivering a totally polyurethane coating composition.
The below Table 1 illustrates that working within the boundaries of select AHEW (amine hydrogen equivalent weight) levels and -OH values of the starting amine-functionalized poly(omega/delta/gamma/beta-hydroxycarbamate) having AHEW in the range of 400 to 5000 and -OH value ranging from 30 to 300 mg KOH/gm after its reaction with urea, favours the desired generation of urea terminated poly(omega-carbamoyloxy urethane) moiety/block based binder, as a reaction product, that is further cured with crosslinkers including regular poly(isocyanate), polyaldehydes, amino resin, urea formaldehyde resin, or mixtures thereof preferably polyalehydes at ambient temperatures to provide for thermoset curing/coating formulations/films thereof with improved drying and sandability with desired hardness performance and gloss characteristics within a short span of time.

Table 1
AHEW OH VALUE mg KOH/gm PERSOZ Hardness(CYCLE)
1700-1800 70-80 128
1500-1600 90-100 121
1500-1600 52-60 138

Below Table 2 shows comparative study revealing the hurdles encountered when the desired range of AHEW of 400-5000 and –OH value ranging from 30 to 300 mg KOH/gm of the starting amine-functionalized poly(omega/delta/gamma/beta-hydroxycarbamate) is not met.

Table 2
AHEW -OH value mg KOH/gm Observations during curing of the product urea terminated poly(omega/delta/gamma/beta-carbamoyloxy urethane)
Below 400 30-300 Gel formation during mixing with hardener
Above 5000 30-300 cheesy even after 72 hours, hardness does not develop
400-5000 Below 30 Tacky after 72 hrs
400-5000 Above 300 Gel formation during curing of the product urea terminated poly(omega/delta/gamma/beta-carbamoyloxy urethane)

Therefore it can be clearly seen that working within the select boundaries of select AHEW (amine hydrogen equivalent weight) levels and -OH values of the starting amine-functionalized poly(omega/delta/gamma/beta-hydroxycarbamate) having AHEW in the range of 400 to 5000 and-OH value ranging from 30 to 300 mg KOH/gm after its reaction with urea, favours the desired generation of urea terminated poly (omega/delta/gamma/beta-carbamoyloxy urethane) based binder whose industrial utility based on its having high urethane crosslinking density achieved in a branched fashion results in fast curing, surface dry and sandability (5 hours or less) and also overnight hardness buildup surprisingly in spite of having large oil backbone in the resultant coating that still maintains high gloss and wet look, contraposed to the general notion that the oils based backbones provides high gloss and wet look upon slow drying and the fast drying characteristics being generally known to take away the gloss building capability of oil based alkyds resulting into relatively mat surface finish.
The advantages and the distinctive directions of the present invention are as follows:
i. The carbamate derivatization of the multiplicity of hydroxyl group have helped to associative tendency thereby enhancing it’s solubility and viscosity stabilization by using protic solvent;

ii. While ambient cross-linking of amine terminated HNIPU with same polyaldehyde conventionally gives rise to immine functionality generation which leads to intensification of colour of the binder in the yellow to red zone. Carbamate derivatization of HNIPU in accordance with the present invention followed by preferably polyaldehyde curing enabled avoidance of abovesaid colour intensification due to conversion of terminal amines into amide and urea successably instead of immine;

iii. The synthesis of carbamate based polymer of the present invention was different from the reported DOW’s(please incorporate the DOW patent application no.) known process. Instead of using methyl carbamate, which is a toxic, hazardous and CMR material, the present invention works with urea, which urea is cost effective and a non-CMR reagent. Besides, the carbamate formation as per Dow’s process of synthesis of the binder generates methanol as by-product, which is a substance for very high concern (SVHC), but the present invention produces ammonia as by-product, which is easily neutralized in an acidic scrubber;
iv. The curing of HNIPU can be done with epoxy rich acrylic resin or alkyd resin under ambient condition. In another way the curing of HNIPU can be done using crosslinkers including polyaldehyde like glyoxal, CHADA etc through imine formation at ambient temperature. Other way the curing of NIPU can also be possible through urea-formaldehyde or amino resin curing route. In another way the curing of NIPU can be done through isocyante route at room temperature or through ester formation at elevated temperature. All these routes are not preferred due to durability or colour issue. To avoid all these undesired routes of crosslinking of HNIPU to provide a thermoset coating film the new curing technology for HNIPU of the present invention via the formation of carbamoyloxy urethane linkage lead to the desired results;
v. The carbamate rich acrylic resin was prepared and it was blended with carbamate functionalized HNIPU of the present invention which when together reacted with CHDA (1,4-cyclohexanedicarboxyaldehyde) as crosslinker in presence of a catalyst curing was observed from sandability of the film after 3-4h;

vi. The added advantages are the carbamate derivatized HNIPU of the present invention was further cured with an acrylic resin in presence of a polyaldehyde through the formation of non-isocyanate polyurethane linkage. The drying, curing efficiency, sandability and re-coatability of the newly cured NIPU system was much better than all other curing technology.

vii. Addition of mass to the binder in the carbamate formation step of the present invention with inexpensive urea also contributes to increase in solids and reduction in cost of the HNIPU binder.

viii. The additional added advantage of simple curing effect from a carbamate rich acrylic with HNIPU is so far not reported as prior art.