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WO2019142208A1 - Fragments de polyhydroxyalkyluréthane non isocyanate durcissables à température ambiante pourvus d'un agent de réticulation aldéhyde - Google Patents

Fragments de polyhydroxyalkyluréthane non isocyanate durcissables à température ambiante pourvus d'un agent de réticulation aldéhyde Download PDF

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Publication number
WO2019142208A1
WO2019142208A1 PCT/IN2019/050032 IN2019050032W WO2019142208A1 WO 2019142208 A1 WO2019142208 A1 WO 2019142208A1 IN 2019050032 W IN2019050032 W IN 2019050032W WO 2019142208 A1 WO2019142208 A1 WO 2019142208A1
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WIPO (PCT)
Prior art keywords
ketone
carbonate
methyl
hnipu
aldehyde
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PCT/IN2019/050032
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English (en)
Inventor
Shaik Allauddin
Kiran Kumar NEHETE
Subarna Shyamroy
B P Mallik
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Asian Paints Ltd.
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Publication of WO2019142208A1 publication Critical patent/WO2019142208A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • TITLE Ambient temperature curable non-isocyanate polyhydroxyalkylurethane moieties with Aldehyde Cross linker
  • the present invention provides for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising: (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer and/or polymer, (ii) hardener comprising“m” number of aldehyde and / or ketone functionalities,“m” being > 1 , adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that“m+n”>4 in said reaction product.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • the present invention also provides for a process for preparation of said coating or curable formulations thereof involving aldehyde and / or ketone functionality based hardening/ cross linking at room temperature for ambient curing and film forming. More particularly, a method of delivering ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is also provided preferably on a substrate wherein said coats/films attained thereof are found to have improved drying and performance properties.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • NIPU Non-isocyanate polyurethanes
  • the main route is a polyaddition of 5-membered cyclic carbonate and diamines leading to the formation of linear/branched PHUs with primary or secondary alcohols, as illustrated in above schemes.
  • the reactive pendant hydroxyl groups enable further post-funtionalization of the PHUs with chemical and biological functionalities.
  • Nonisocyanate polyurethanes disclosed under US 7045577 / 2002A, teaching preparation of novel carbonated vegetable oils (such as carbonated soybean oil) by reacting carbon dioxide with an epoxidized vegetable oil.
  • novel carbonated vegetable oils such as carbonated soybean oil
  • the carbonated vegetable oils are advantageously used therein for producing non-isocyanate polyurethane materials.
  • US 7989553 /2009 relates to three-dimensional epoxy-amine polymer networks modified by a hydroxyalkyl urethane, which is obtained as a result of areaction between a primary amine (one equivalent of the primary aminegroups) and a monocyclic carbonate (one equivalent of the cyclic carbonategroups) .
  • hydroxyalkyl urethane modifier is not bound chemically tothe main polymer network.
  • US8703648, US8975420, US8951933/2009A teaches new polysiloxane-modified polyhydroxy polyurethane resin derived froma reaction between a 5-membered cyclic carbonate compound and an amine modified polysiloxane compound.
  • US Application20150247004 /2014A relates to a method of forming non isocyanate based polyurethane includes providing a cyclic carbonate, an amine, and a cooperative catalyst system that has a Lewis acid and a Lewis base.
  • US4520167 discloses amino-aldehyde diluent cross linker for hydroxypolyurethane structures that cures at elevated temperatures.
  • US7820779 discloses nanostructured hybrid liquid oligomer composition
  • fast curable NIPU and HNIPU polymeric nanocompositions are derived upon crosslinking a mixture comprising of natural or modified nano-clay with either a monomer(s)/ oligomer(s) bearing cyclocarbonate group(s) or a m ixture of the latter with an epoxy resin, with a hardener bearing am ino groups.
  • CN 102093873 discloses a fracture liquid having the advantages of good thermal stability, salt resistance, and shear resistance, and can avoid residual slag of polym er chain group consisting of synthetic polym er 0.1 - 1 , crosslinking agent 0.1 - 1 , clay stabilizer 0.2- 1 , surfactant 0.1 -0.8, oxidant 0.001 - 0.05, and H 2 0 94-99% wherein the synthetic polymer is homopolym er and polym er prepared from acrylam ide monomer, vinyl monom er, and hydrophobic monom er, and its mol. wt. is 500000- 1 0000000 and the crosslinking agent is organic amphoteric metal com plex crosslinking agent and/or aldehyde crosslinking agent.
  • DE291 1 062 discloses adducts of glyoxal or glutaraldehyde with polyols ( D- glucose, maltose, sucrose, amylose, glycerol) useful as molding composition binders (e.g., for sand molds) , in surfactants, and crosslinking agents which give control crosslinking of other polyhydroxycom pounds.
  • polyols D- glucose, maltose, sucrose, amylose, glycerol
  • molding composition binders e.g., for sand molds
  • crosslinking agents which give control crosslinking of other polyhydroxycom pounds.
  • Aldehydes crosslink with cellulosic polyols at high temperature is disclosed.
  • GB807851 teaches heat-resistant phenolic resins prepared by form ing the polybasic inorganic acid partial ester of a polyhydroxy aromatic compound having an unsubstituted position reactive with HCHO by reaction with H 3 B0 4 , H 3 P0 4 , or POCI 3 with heating in such a m anner that a substantial proportion of the phenolic OH groups rem ains unreacted, and then curing at an elevated tem perature with an aldehyde or compound that decomposes to an aldehyde takes place.
  • FR1478229 discloses urethane m ethylol ethers containing free OH groups prepared by treating 8-hydroxyethyl carbamates with HCHO at pH > 7 and etherifying with an aliphatic monoalcoholic at pH ⁇ 7.
  • the compounds are used to prepare crosslinked polyurethane resins, as paper additives to increase the tear and wet resistance, in paper glues, as textile additives, and as aging protectors and stabilizers for synthetic resins wherein 8-hydroxyethyl m ethoxymethyl carbam ate, Me0CH2NHC02CH2CH20H, which on treatment with HCHO gave m ethylene bis ( 8-hydroxyethylurethane N- methylol methyl ether) wherein the aldehyde reacts with the amido end of a beta-hydroxyethyl carbamate and the hydroxyethyl group is etherified with an alcohol.
  • CN 104710642 discloses a kind of surface modifier of the polyurethane film and preparation method thereof.
  • the surface modifier of the polyurethane film is aqueous solution of fluorosilicone-containing dialdehyde wherein the surface gets modified by using a photoinitiator that strengthens the performance of the polyurethane film .
  • CN 104693777 teaches an anti-scratch polyurethane film and its preparation method comprising mixing the fluorosilicone-containing dialdehyde, photoinitiator and water to form uniform solution to prepare the polyurethane film surface modifier; uniformly coating the polyurethane film surface modifier on the polyurethane film surface, carrying out UV-irradiation for initiating the crosslinking curing reaction, and drying to obtain the anti-scratch polyurethane film.
  • the primary object of the present invention is to provide for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof which in comprising selective binder and hardener functionalities would be room temperature curable by aldehyde and/ or ketone functionalities employed as hardener/ cross-linker adapted for ambient curing together with improved drying and performance properties.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • Another object of the present invention is to provide for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof which in comprising selective binder involving selective amine content together with select number of hydroxyurethane repeat units in said oligomer/ polymer would be free of any requirement of polymerizable unsaturated groups in the binder such as vinyl, acrylic, acrylamide type groups and yet be curable at room temperature by hardener functionalities involving aldehyde and / or ketone functionalities used as a cross-linker.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • Another object of the present invention is to provide for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof providing for a reaction product of a select binder and aldehyde and / or ketone functionality based hardener that would be free of phenolic -OH groups and polymerizable unsaturated groups such as vinyl, acrylic, acrylamide type groups and yet would show improved drying and performance properties.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • Yet another object of the present invention is to provide for a process of manufacture of said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations that would facilitate cured coat or curable form ulationsas a reaction product of said binder and hardener in the temperature range of about -5 to 40 °C.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • Still another object of the present invention is to provide for a process of manufacture of said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof which process would be free of any photoinitiator based curing conditions and yet would be performable under ambient/ room temperature conditions.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • an ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising:
  • a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having the following structures (I) below
  • n> 2; x 0-4;
  • R 1 R2,R 3 , and R 5 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;
  • R 4 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
  • hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being >1, adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that“m+n”>4 in said reaction product.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof could be attained of : (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer and/or polymer, and (ii) hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being >1, surprisingly providing said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that when “m+n”>4 in said reaction product.
  • a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine
  • ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof wherein said “m” number of aldehyde and/or ketone functionality based hardeners comprise selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided which is either a coating comprising ambient cured reaction product of said (i) and (ii), or, is a formulation comprising ambient curable ready to apply said (i) and (ii) as components of a formulation favouring generation of said reaction product based coating.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof having said binder and / or hardener sourced total aromatic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is provided wherein said aromatic content is chemically connected with the HNIPU binder and is sourced from the groups selected from the group consisting of one or more aromatic polyamines, one or more aromatic epoxy resins, one or more epoxy functional polymers, one or more benzene ring containing polymers, one or more polyanhydrides, one or more anhydride functional polymers and combinations thereof.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof wherein said hardener comprises“m” number of aldehydeand/ or ketone functionalities;
  • said binder base comprises amines and/or imine reacted polycyclic carbonate and/or cyclic carbonate based (HNIPU) binder
  • said polycyclic carbonate and/or cyclic carbonate includes reaction products of at least one aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.
  • an ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof wherein said hardener comprises aldehyde functionality based aldehyde compound such that “m” >1 including aqueous, non-aqueous, neat liquid and solvent-borne polyaldehydes comprising acetal adduct of polyaldehyde and alcohols/glycols, schiff base adduct of polyamine/polyimine and polyaldehyde having “m” number of free aldehyde functionalities per adduct molecule including alkyl, aryl or aliphatic, cyclo aliphatic radicals that may include 1-30 or higher carbon atoms, linear and/or branched moieties, one or more hetero atoms containing functionality and includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof wherein said hardener comprises at least one or more ketone functionality based ketone compound such that “m” >1 including mono-, d i - , tri- and poly-ketone compounds, said monoketones including Methyl isobutyl ketone, Dicyclohexyl ketone, Methyl 2-pyrrolyl ketone, 2-Furyl methyl ketone, Cyclohexyl phenyl ketone, 3-Flepten-2-one, Ethyl vinyl ketone, Di ( 2 - pyridyl) ketone, Po I y ( v i n y I methyl ketone), Bis(1 -methyl-2-imidazolyl) ketone, Di-2-thienyl ketone, 1 - Isoquinolinyl phenyl
  • Methylglyoxal 1,1 -dimethyl acetal 4-Methylbenzophenone, 1,1- Dichloro-2- propanone, Benzophenone-3,3' ,4,4' -tetracarboxylic dianhydride, 3-Hydroxy-1 ,2- dimethyl-4(1 H)-pyridone, Ethyl 2-oxo-1 -cyclooctanecarboxylate, 1-Methyl-2- pyrrolidinone,1 - Benzyl -2- pyrrol id i none, N- Methyl pyrrol idone, 4- Hydroxy- 4- methyl - 2-pentanone; 2,2,6,6-Tetramethyl-4-piperidone,Diacetone amine Triacetone amine, ACETYLACETONE IMIDE;
  • Di-ketones including 1 ,3- Dibenzoylpropane ,1,2-diketone (diacetal), 1,3- diketone (acetylacetone) , 15,4-diketone (hexane-2, 5-dione), 1,2- Naphthoquinone, 2-Methyl-1 , 4- naphthoquinone, 1 ,3- Dibenzoylbenzene, 2- Acetylcyclopentanone,4-Cyclopentene-1 ,3-dione, 4,5-DICHLORO-4-
  • said triketone including 2-acetyl-1 -methoxy-anthraquinone, cycloheximide, actiphenol;
  • polyketones including Po I y ( v i n y I methyl ketone), polyketones,
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof wherein said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1 ,6-hexamethylene diamine; 1 ,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine) ; 2- methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1 ,3-propanediamine, bis- (4,4’- aminocyclo hexyljmethane, tricyclo
  • IPDA isophorone diamine
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided wherein said cyclic ether precursors to polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/polymers thereof.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof wherein said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerine carbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl)-ethylene carbonate, 3,4-0-isopropylidene-D-mannitol-1 ,2:5,6- dicarbonate and D-mannitol-1 ,2:5, 6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-1 ,3-dioxolan-2-one, 4-Trifluoromethyl-1 ,3-dioxolan-2-one, bisphenol A polycarbonate, Divinylbenzene Dicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene
  • ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or formulations thereof is provided adapted for clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • a binder base comprising (i) ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of amine hydrogen equivalent weight in the range of 400-1600 and having the following structures (I) below
  • n> 2; x 0-4;
  • R 1 R 2 ,R3, and R 5 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;
  • R 4 comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; b) having a hardener comprising “m” number of aldehyde and / or ketone functionalities,“m” being > 1 ; c) mixing said binder (a) with said hardener(b) and allowing the mixture to dry at ambient temperature of -5 to 40 °C to provide for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (a) and (b) such that m+n>4 in said reaction product.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • said step (b) of having a hardener comprises having “m” number of aldehyde and / or ketone functionality based hardeners including selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.
  • said binder and/ or hardener sources total arom atic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product.
  • said step (a) of having a binder comprising ambient tem perature curable hydroxyl urethane oligomer and/or polym er (HNI PU) binder includes reacting polycyclic carbonate and/or cyclic carbonate with am ines and/or im ines in stoichiometric equivalents in the range from 1 : 0.4 to 1 : 2.2 respectively to yield a polymer with hydroxyurethane ( PHU) groups having am ine equivalent weight in the selective range of 400- 1 600.
  • said polycyclic carbonate and/or cyclic carbonate is sourced from reactions between aryl or alkyl carbonate and diol/ glycol ; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precu rsors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.
  • said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerine carbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl) - ethylene carbonate, 3, 4-0- isopropylidene- D-m annitol- 1 ,2: 5, 6-dicarbonate and D- mannitol- 1 ,2:5, 6-dicarbonate, isosorbide based bis-cyclic carbonate, 4- Phenyl-
  • 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-
  • said cyclic ether precursors for generation of polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/ polymers thereof.
  • said hardener comprises aldehyde functionality based aldehyde compound such that “m”>1 including aqueous, non-aqueous, neat liquid and solvent-borne polyaldehydes comprising acetal adduct of polyaldehyde and alcohols/glycols, schiff base adduct of polyamine/polyimine and polyaldehyde having “m” number of free aldehydefunctionalities per adduct molecule includingalkyl, aryl or aliphatic, cyclo aliphatic radicalsthat may include 1-30 or higher carbon atoms, linear and/or branched moieties, one or more hetero atoms containing functionality and includes 3-4 dimethoxy benzaldehyde, 2-5 Diformylfuron Furfural Glutaraldehyde solution 25% in water, Glyoxal solution 40% in water; 4-5 dimethyl 2 furaldehyde; PARALOIDTM EDGE X
  • said hardener comprises at least one or more ketone functionality based ketone compound such that “m” >1 including mono-, d i - , tri- and poly-ketone compounds, said monoketones including Methyl isobutyl ketone, Dicyclohexyl ketone, Methyl 2-pyrrolyl ketone,
  • Nonanone sovalerophenone 1 ,3- Diphenyl-2-propanone, 2-Aminobenzophenone,
  • Di-ketones including 1 ,3- Dibenzoylpropane, 1,2-diketone (diacetal), 1,3- diketone (acetylacetone) , 15,4-diketone (hexane-2, 5-dione), 1,2- Naphthoquinone, 2-Methyl-1 , 4- naphthoquinone, 1 ,3- Dibenzoylbenzene, 2-
  • said triketone including 2-acetyl-1 -methoxy-anthraquinone, cycloheximide, actiphenol;
  • polyketones including Po I y ( v i n y I methyl ketone), polyketones,
  • Preferably said method of providing for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof as clear coat or pigmented coat includes one or more polymer blend, additives, fillers, extender and optionally pigments.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • a method of delivering ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising: i. Having a base binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having the following structure (I) below
  • n> 2; x 0-4;
  • R 1 .R 2 .R 3 , and R 5 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;
  • R 4 comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moietiescontaining 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and ii. Having a hardener comprising “m” number of aldehyde and / or ketone functionalities,“m” being > 1
  • step (iii) Applying coating of the above mixture of step (iii) above on a substrate to thereby deliver ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating upon drying at ambient temperature of -5 to 40°C based on generation of a reaction product having m+n >4 in said reaction product.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • said hardener of step (ii) comprises said“m” number of aldehyde and/or ketone functionality based hardeners comprising selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.
  • said substrates include Metal, Wood, Plastic, Aluminum, Glass, Paper, Gypsum, Cement, Porus bricks, Sand, and wherein said method includes either delivering the coating directly on any of these substrates or on top of a suitable primer, and also includes top-coating said coating with any other type of binder said coating provided as a topcoat or undercoat being either a clear-coat or a pigmented coat.
  • said applying the coating includes applying by brush, spray, roller, spin coater, bar coater, applicator, poring, impregnating, dipping in resin, wounding of solid resin on said substrate.
  • the present invention provides for ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising: (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) as the select binder of selective amine hydrogen equivalent weight in the range of 400- 1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer/ polymer, (ii) hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being >1, adapted for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that “m+n”>4 in said reaction product.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • the present invention also provides for a process for preparation of said coating or curable formulations thereof involving aldehyde and / or ketone functionality based hardener for cross linking with said select binder at room temperature curing or film forming, which coats/ films have improved drying and performance properties.
  • select polymeric/ oligomeric binder (HNIPU)s of the present invention of select amine equivalent weight in the range of 400-1600 comprises following structure(l) below
  • R 1 R2,R 3 , and R 5 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; R 4 comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and Said select hardener comprises “m” number of aldehyde and / or ketone functionalities,“m” being >1 and upon mixing said binder (I) with said hardener and further allowing the mixture to dry at ambient temperature of -5 to 40 °C provides for said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU
  • said “m” number of aldehyde and/or ketone functionality based hardeners comprise selectively at least one aldehyde compound, ketone compound, compounds with both aldehyde and keto functionality.
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof is either a coating comprising ambient cured reaction product of said (i) and (ii), or, is a formulation comprising ambient curable ready to apply said (i) and (ii) as components of a formulation favouring generation of said reaction product based coating.
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprise select binder functionalities of selective amine content together with select hydroxyurethane repeat units in said binder oligomer/ polymer that is further free of any requirement of polymerizable unsaturated groups in the binder such as vinyl, acrylic, acrylamide type groups to be curable at room temperature by aldehyde and / or ketone functionalities used as a hardener/cross-linker adapted for improved drying and performance properties of said coats/films in terms of gloss, hardness and scratch resistance.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising a reaction product of selective amine content and selective hydroxyurethane repeat units based HNIPU oligomer/ polymer with aldehyde and / or ketone functionalities, which NIPHU is free of phenolic -OH groups and polymerizable unsaturated groups such as vinyl, acrylic, acrylamide type groups and yet shows improved drying and performance propertiesin terms of gloss, hardness and scratch resistance.
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • HNIPU ambient cured hydroxyl non-isocyanate polyurethane
  • a process for preparation of ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising the steps of : providing HNI PUs oligomer/ polym er comprising select binder functionalities of selective am ine content together with select hydroxyurethane repeat units in said NI PHU oligom er/ polym er; further providing a hardener comprising aldehyde and / or ketone functionalities; m ixing said binder with said hardener and allowing the m ixture to dry at am bient temperature of -5 to 40 °C to provide for said ambient cured hydroxyl non-isocyanate polyurethane ( HNI PU) based coating having a reaction product of said (a) and (b) such that m+ n> 4 in said reaction product.
  • said reaction product is formed at room tem perature and free of any photoinitiators to obtain therefrom said aldehyde and / or ketone functionalities cured HNI PUs with improved drying and performance propertiesin terms of gloss, hardness and scratch resistance.
  • the select binder com prising ambient temperature curable hydroxyl urethane oligomer and/or polym er (HNI PU) binder of the present invention having the above structure ( I) is obtained according to an embodiment of the present invention :
  • polycyclic carbonate and/or cyclic carbonate by reacting polycyclic carbonate and/or cyclic carbonate with amines and/or im ines in stoichiometric equivalents in the range from 1 : 0.4 to 1 :2.2 respectively to yield a polym er with hydroxyurethane ( PHU) groups having am ine equivalent weight in the selective range of 400- 1 600.
  • PHU hydroxyurethane
  • said polycyclic carbonate and/or cyclic carbonate is sourced from reactions between aryl or alkyl carbonate and diol/ g ly col ; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cylic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.
  • the ambient cured hydroxyl non- isocyanate polyurethane ( HNI PU) based coating or curable form ulations thereof comprising said hydroxy-NI PUs (non-isocyanate polyurethanes, HNIPUs) binder is characterized by:
  • AHEW selective amine hydrogen equivalent weight
  • Viscosity [Gardner-Holdt (Units)] in the range of: K-L to Z7-Z8,
  • hydroxy-NIPU binder (HNIPUs) involving unreacted terminal amine groups is optionally reacted with anhydride and / or epoxy and / or acid functionalities.
  • said binder and / or hardener sources total aromatic content in the range of 3 to 30 wt.% defined by the wt.% of a single benzene ring residue with respect to the total solids of the cured product.
  • Said aromatic content being chemically connected with the HNIPU binder and is sourced from the groups selected from the group consisting of one or more aromatic polyamines, one or more aromatic epoxy resins, one or more epoxy functional polymers, one or more benzene ring containing polymers, one or more polyanhydrides, one or more anhydride functional polymers and combinations thereof.
  • said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof reveals improved drying and performance properties.
  • said coat/ formulation shows fast drying system at room temperature by uniform formation of glossy filmswith hardness and scratch resistance.
  • said binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binderinvolving unreacted terminal amine groups of said binder is optionally reacted with anhydride and / or epoxy and / or acid functionalities.
  • HNIPU ambient temperature curable hydroxyl urethane oligomer and/or polymer
  • both aromatic and non aromatic binder backbone can advantageously result in tack-free surfaces on wood panels when applied onto it, subject to the fulfillment of amine hydrogen equivalent wt. (AHEW) of the binder to be within the select range.
  • AHEW amine hydrogen equivalent wt.
  • the binder remained tacky for much longer period, even beyond 100 hrs, which is less desirable.
  • Tables 1 and 2 above relates to improved drying properties attained, the performance properties also gets significantly enhanced.
  • Table 4 Coating properties of cross linked HNIPUs with aldehyde and / or ketone functionalities involving different aldehyde molecules on wood panels when amine hydrogen equivalent wt. of the binder is in the range of 400 - 1600 and ‘m+ n’ >4.
  • Table 5 Coating properties of cross linked HNIPUs with different aldehyde molecules on metal panels when amine hydrogen equivalent wt. of the binder is in the range of 400- 1600 and ‘m+n’ >4.
  • ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating or curable formulations thereof comprising: (i) a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder of selective amine hydrogen equivalent weight in the range of 400-1600 and having n>2, ‘n’ being the number of hydroxyurethane repeat units in said oligomer and/or polymer, and (ii) hardener comprising “m” number of aldehyde and / or ketone functionalities, “m” being 3 1 ,su rprisi ng ly providing said ambient cured hydroxyl non-isocyanate polyurethane (HNIPU) based coating having a reaction product of said (i) and (ii) such that “m+n”>4 in said reaction product.
  • a binder base comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU)
  • a process for preparation of said coating or curable formulations thereof are also provided involving aldehyde and / or ketone functionality based hardening/ cross linking at room temperature for ambient curing and film forming, wherein said coats/films are found to have improved drying and performance properties.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un revêtement à base d'hydroxypolyuréthane non isocyanate durci à température ambiante (HNIPU) ou des formulations durcissables correspondantes, comprenant : (i) une base de liant comprenant un liant oligomère et/ou polymère d'hydroxyuréthane durcissable à température ambiante (HNIPU) d'un poids équivalent d'hydrogène d'amine sélectif dans la plage de 400-1600 et possédant n ≥ 2, 'n' étant le nombre de motifs récurrents d'hydroxyuréthane dans ledit oligomère et/ou polymère, (ii) un durcisseur comprenant un nombre "m" de fonctionnalités aldéhyde et/ou cétone, "m" étant ≥ 1, conçu pour que ledit revêtement à base d'hydroxypolyuréthane non isocyanate durci à température ambiante (HNIPU). Selon l'invention, il présente un produit de réaction de (i) et de (ii) de sorte que "m + n" ≥ 4 dans ledit produit de réaction. L'invention concerne également un procédé de préparation dudit revêtement ou desdites formulations durcissables correspondantes, impliquant un durcissement/une réticulation sur la base de la fonctionnalité aldéhyde et/ou cétone à température ambiante pour le durcissement et la formation de film à température ambiante.
PCT/IN2019/050032 2018-01-16 2019-01-12 Fragments de polyhydroxyalkyluréthane non isocyanate durcissables à température ambiante pourvus d'un agent de réticulation aldéhyde WO2019142208A1 (fr)

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CN112441898A (zh) * 2019-08-27 2021-03-05 捷恩智株式会社 二醛化合物、聚合物、环氧树脂、聚酯树脂及聚碳酸酯树脂
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CN113999606A (zh) * 2021-12-30 2022-02-01 科顺防水科技股份有限公司 聚氨酯防水涂料及其制备方法
CN114380980A (zh) * 2021-12-01 2022-04-22 西北工业大学 自修复有机硅弹性体材料及其制备方法
CN115926109A (zh) * 2022-10-24 2023-04-07 东华大学 一种基于铜离子配位的咪唑脲键自愈合弹性体
WO2023183081A1 (fr) * 2022-03-23 2023-09-28 Rockytech, Ltd. Polyhydroxyuréthanes et leurs procédés de fabrication et d'utilisation
CN119505516A (zh) * 2024-11-18 2025-02-25 常州市第一人民医院 一种人工半月板及其制备方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112441898A (zh) * 2019-08-27 2021-03-05 捷恩智株式会社 二醛化合物、聚合物、环氧树脂、聚酯树脂及聚碳酸酯树脂
CN111471174A (zh) * 2020-05-14 2020-07-31 苏州欧纳克纳米科技有限公司 一种自干型水性非异氰酸酯聚氨酯
WO2022011544A1 (fr) * 2020-07-14 2022-01-20 Dow Global Technologies Llc Composés polyols et compositions adhésives préparées à l'aide de ceux-ci
CN114380980A (zh) * 2021-12-01 2022-04-22 西北工业大学 自修复有机硅弹性体材料及其制备方法
CN113999606A (zh) * 2021-12-30 2022-02-01 科顺防水科技股份有限公司 聚氨酯防水涂料及其制备方法
WO2023183081A1 (fr) * 2022-03-23 2023-09-28 Rockytech, Ltd. Polyhydroxyuréthanes et leurs procédés de fabrication et d'utilisation
CN115926109A (zh) * 2022-10-24 2023-04-07 东华大学 一种基于铜离子配位的咪唑脲键自愈合弹性体
CN119505516A (zh) * 2024-11-18 2025-02-25 常州市第一人民医院 一种人工半月板及其制备方法

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