Claims:We Claim:
1. 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols comprising
Polyester polyol as a reaction product of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid (55-85%), anhydrides/diacids and diol/polyols; wherein said diacids and/or anhydride is in select ratio of 0.1:1 to 0.7:1 with respect to hydroxy equivalent of said 12-hydroxy-9-cis-octadecenoic enriched fatty acid, said polyester polyol having hydroxyl value in the range of 100-280 mg KOH/g, acid value in the range of 0-20 mg KOH/g, and molecular weight (Mn) in the range of 400-2000 daltons.
2. 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claim 1 suitable for coating including wood coating, waterproofing membrane, cementitious waterproofing and floor coatings (car deck, bridge deck) including industrial coatings providing excellent hydrophobicity, chemical resistance and mechanical performance based on improved tensile strength, elongation, chemical resistance, gloss and are suitable for brush or roller or spray applications when thinned with solvent.
3. The 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claims 1 or 2 that is solvent less flow-able polyester polyol wherein for desired tensile strength (1.0-11 Mpa) - % elongation (10-500%) balance, said anhydride/ diacids including aromatic/aliphatic anhydride/diacid involves at least one anhydride/diacid selected from phthalic anhydride, adipic acid, sebacic acid cyclohexane dicarboxylic acid (CHDA), tetrahydro phthalic acid, hexahydro phthalic acid or anhydride, maleic anhydride or combinations thereof, and,
wherein said diol/polyol includes both linear and branched alcohols as at least one diol selected from ethylene glycol, 1 ,2- propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,4-butanediol, 1 ,3-butanediol, 2,2- dimethyl-1 ,3-propanediol (= neopentyl glycol), 2,5-hexanediol, 1,6-hexandiol, 2,2-[bis- (4-hydroxy-cyclohexyl)]-propane, 1, 4-dimethylol cyclohexane, diethylene glycol and dipropylene glycol, and combinations thereof. whereas multi-functional alcohols include glycerol, hexanetriol, pentaerythritol, sorbitol, trimethylol ethane (TME), ditrimethylol propane, rimethylol propane (TMP) and combinations thereof, preferably NPG, HDO and TMP and combinations thereof; enabling said 12 hydroxy-9-cis-octadecenoic acid enriched polyester polyols having acid value preferably in the range of 0-5 mg KOH/g and molecular weight (Mn) preferably in the range of 500-1500 daltons.

4. The 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claims 1-3 wherein said polyester polyol is preferably a reaction product of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid 55-85%, Anhydride/Diacid 5-30%, and Diol/polyol 4-30%; favouring processable viscosity in the range of from 600 to 1200 poise at temperatures of 25 ?C for diverse coating formulations; and also allowing blending of said polyester polyols additionally with 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid for increased pot life free of any viscosity issues to require solvent dilution.

5. The 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claims 1-4 wherein in said polyester polyol involvement of petroleum derived polyether polyol or elastomeric polyol is reduced from 10-25% to 0-2% and involvement of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid is maximized such as to enable said processable viscosity free of any solvent dilution, and also enables tensile strength (1.0-11 Mpa)/ elongation (10-500%) balance together with high hydrophobicity and good reactivity.

6. The 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claims 1-5 for incorporation in coating formulations either individually or as a combination of two different polyester polyol including ambient curing coatings, baked and thermoset coatings based on hardeners/ curing agents including polyisocyanates, urea-formaldehyde, melamine-formaldehyde wherein when the desired -OH value of said polyester polyol is 100-200 mg-KOH/g hardener for baking includes amino resin to favour thermoset coating, and wherein when the desired -OH value of said polyester polyol is 100-280 mg-KOH/g hardener for amino baking includes melamine formaldehyde resin and for PU includes Isocyanates (TDI, IPDI, HDI, polymeric MDI etc) and urea formaldehyde as curing agents.
7. A process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claims 1-6 based on condensation polymerization free of any involvement of esterification catalyst and azeotrope solvent comprising the steps of
(i) Providing for reaction 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid (55-85%), anhydrides/diacids, and diol/polyols with said diacids or anhydride in select ratio of 0.1:1 to 0.7:1 in respect of hydroxy equivalent of said 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid; and
(ii) obtaining therefrom 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols having hydroxyl value 100-280 mg KOH/g and acid value 0-20 mg KOH/g with molecular weight (Mn) levels of 400- 2000 daltons.

8. The process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claim 7 wherein said step (i) of providing 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid, anhydrides/diacids, and diol/polyols for reaction in said ratios and equivalents involves:
reacting by heating and refluxing at 170-185°C with continued heating till 220-230°C with constant removal of water of reaction by Dean-stark apparatus and after removal of 90% of water of reaction, monitoring acid value and viscosity of the resin every half an hour to reach to acid value in the range of 3-7 mg KOH/g and viscosity in the levels of 600-1200 poise at temperatures of 25 ?C, followed by cooling the batch to 100°C for discharge in a metal container thereby obtaining said low viscosity resin with excellent tensile strength and elongation.
9. The process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claims 7 or 8 wherein
said step (i) preferably involves 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid 55-85% along with at least one Anhydrides/Diacids 5-30%, and at least one Diol/polyols 4-30%, as reactants, for reacting under nitrogen providing to thereby obtain said 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols having hydroxyl value in the range of 100-280 mg KOH/g and acid value 0-20 mg KOH/g, molecular weight (Mn) 400- 2000 daltons and low processable viscosity in the range of from 600 to 1200 poise at temperatures of 25 ?C to favour diverse coating formulations.
10. The process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols as claimed in claims 7-9 wherein followed to cooling the polyester polyol batch to 100°C for discharge in a metal container, the same is additionally blended with 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid to favour increase in pot life free of any viscosity issues and free of requiring any solvent dilution.

Dated this the 31st day of March, 2022 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
IN/PA-199

, Description:Field of the Invention:
Present invention relates to high content 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid composition based polyester polyol system with high hydroxyl value suitable for coating application and synthesis thereof. More particularly the present invention relates to synthesis of high 12-hydroxy-9-cis-octadecenoic acid based solvent free polyester polyol system with high hydroxyl content suitable for two component coating for brush or roller applications, optionally the resin can also be thinned with solvent for spray applications. Said high 12-hydroxy-9-cis-octadecenoic acid based polyester polyol resin is especially useful as coating for car deck, bridge deck, waterproofing and construction purposes. The resin can also be used for wood coating, industrial coatings etc.
Background of the Invention
Polyurethane (PU) coatings are widely known for their versatility of application with many advantages over the conventional coating systems. Based on the raw materials used i.e. the composition of the polyol used for polyurethanes are classified into two types- polyester and polyether. These two types of polyurethane elastomers have their own advantages and disadvantages. Polyester polyurethanes have excellent mechanical properties such as: tensile strength, tear strength and oil resistance, etc., but due to the high ester bond in the structure, the hydrolysis resistance of the product is relatively poor; whereas polyether polyurethane elastomer has the characteristics of ether bond in the molecule, hydrolysis resistance is good, but mechanical performance is poor.
Further PU coatings can be divided into one pack and two pack systems, wherein the one pack system contains a dissolved fully reacted PU or blocked isocyanate, while the two pack system can contain various types of polyols, varying in functionality, chain length and backbone in one pack and isocyanate in the other pack.
Both these systems can be further classified as solvent based, water based or solvent free systems. The solvent free polyurethane system offers several advantages over the solvent based system as they are environmental friendly (due to very low volatile organic compound content) and have a wide range of superior properties such as chemical resistance (due to eliminated solvent entrapment and less permeability), impact strength, and high build application in single coat apart from coating varied number of substrates. Better impermeability also helps in longer corrosion protection by making the coated film a better barrier to water vapour.
In an endeavor, to replace the conventional petroleum-based polyurethane (PU) coatings with bio-based polyurethane coatings most sought after option is utilization of bio-based materials, including vegetable oils and their derivatives such as methyl ester, fatty acid, and other bio-renewable sources. References are invited for few related prior arts:

WO 96/06123, U.S. Pat. No. 5,512,655 describes the modification of castor oil with epoxy and there by reaction with glycols to achieve hydrophobic polyol where concentration of castor oil is not more than 50%. EP 0798325 describes a polyol that is obtained when castor oil is reacted with aromatic polyester.
US 2002/0035235 A1, describes a polyol where castor oil is modified with stoichiometric excess of anhydride or polyacids to form an acid terminated pre polymer intermediate in the first stage, and followed by reaction with aliphatic alcohols in the second stage to generate primary hydroxyl based polyol.
U.S. Pat. No. 4,608,203 describes a polyurethane coating for bridge concrete where polyol is a mixture of poly (propylene oxide), glycerol and acrylonitrile-butadiene copolymer with MDI to get desired hydrophobicity and mechanical performance.
US4855185 describes polyurethane bride decking composition where low molecular weight polyol is blended with elastomer to achieve desired tensile and elongation.
U.K. Pat. No. 1,182,884, Gruber and Fehlbier (1970) describes treatment of castor oil with cyclohexanone formaldehyde condensate, thereby providing modified castor oil as used herein. Reaction of the modified castor oil with MDI to make a polyurethane resin is also disclosed.
US20020035235A1 describes a polyhydroxyl composition derived from castor oil for flooring, coating and adhesive application, which is highly reactive at low temperature. The process of preparing polyol is half ester process and polyols are obtainable by the reaction of fatty acid or ester of a fatty acid with anhydride of a dicarboxylic acid in the presence of an esterification catalyst and heating wherein final esterification is carried out with polyhydroxyl compound at 230° C. to 250° C. The polyhydroxy compound is having hydroxyl equivalent is from 150 to 250.Forthe polyester polyols the ratio between anhydride and hydroxy-equivalent of castor oil is from 0.5:1 to 2:1.
US 2004/0186247 discloses coating compositions comprising polyester polyols- which is prepared from polyol, cyclic polycarboxylic acid and at least one monocarboxylic acid. In this case, it is taught that the polyol must have a hydroxyl value in the range of 200-400 mg KOH/g. All of the coating compositions disclosed in US2004/0186247 are cured above ambient temperature, at 60° C., and all have a high Volatile Organic Content (VOC) of greater than 300 g/l.
US10155837 describes a castor oil based polyester polyol with hydroxyl value 20-150 derived from digested PET, 25-85% castor oil, glycols and diacid (optional). The polyester polyol is used for rigid foam application
US9809674 describes about high functional polyester polyols for foam application having hydroxyl value 320-400 mg KOH/g
US9688878B2 describes a 70% NVM polyester polyol along with a curing agent, whereas tri or more functional polyol and C6-C20 monobasic fatty acids are used to prepare a polyol with hydroxyl value 60-200 mg KOH/g and Mn 100¬0-5000 daltons for a coating composition having a solids content of greater than 70% by weight and/or a Volatile Organic Content (VOC) of less than 250 g/l,
US20040081830A1 relates to a polyurethane surface derived from the catalyzed reaction of a polyisocyanate component and an active hydrogen component wherein the compound having active hydrogen atoms comprises a solution of one polyester polyol and one polyether polyol and said polyester polyol is castor oil. The two-component system achieves optimal gel time and cure response for application as an athletic surface.
US6087469A describes about a low molar mass polyester polyol (Mn<2000) with hydroxyl value 80-30 mg KOH/g, prepared from aliphatic polycyclic polyhydroxy compound, branched aliphatic acyclic diols, aliphatic cyclic diacids, aliphatic acyclic/monocyclic tri- or tetra-ols, monofunctional acids or alcohols. It is used for spray application where low dilution is required.
CN112574403A describes a castor oil based polyol for solvent free adhesive, having hydroxyl value 150-200 mg KOH/g, AV < 2 mg KOH/g. The polyester polyol is prepared from castor oil, small diacid, ionic reactive monomer and low molecular weight polyether polyolsuch asPPO polyether polyol, PEG polyether polyol (both having hydroxyl value of 200-500mgKOH/gor polytetrahydrofuran polyether polyol (hydroxyl value of 160-600mgKOH/g). The resultant polyester is low cost and high stable.
WO2001025184A1 relates to transesterification polyols which are produced from ricinus oil and native trigycerides that are free of OH-groups and which are suitable for use as polyols for producing polyurethane prepolymers.
CN107488434A provides a 1:1 quick-drying spraying two-component polyurethane adhesive for door manufacturing, integrated plate manufacturing, insulation material production comprising self-prepared polyester polyol, polyether polyol, utilizing castor oil, glycerine, phthalic anhydride for synthesis and its Middle molar ratio of alcohol to acid, i.e. castor oil:small molecular alcohol (glycerine, phthalic anhydride) is 1:1.8 and acid number=2mgKOH/g.
CN104130690Arelates to water-proof wear-resistant insulation coatings for use in trains, which comprises modified polyester polyol ricinoleate, rubber powder, wear-resistant filler, catalyst etc., and 20-40 parts isocyanate curing agent. The modified polyester polyol ricinoleate is prepd. by reacting 60-80 ricinoleic acid, 10-30 polyol, 5-10 part phthalic anhydride in presence of esterification catalyst.
EP1584656A1 teaches for an epoxide-free non-toxic composition for coating metals, esp. interiors of food containers comprises phenolic resins and branched, based on castor oil olefinically unsaturated polyesters having free carboxyl groups (made of dicarboxylic acids, polyols and monocarboxylic acid) at polyesters-phenolic resins ratios (50 - 90):(50 - 10).
EP1178060A1 Polyester polyols obtainable by half-ester formation from one dicarboxylic acid anhydride, and one OH group carrying fatty acid preferably castor oil and/or ricinoleic acid, and post-esterification via at least one polyol. The synthesized polyester polyols having acid value more than 200 are used in formulation of reactive polyurethane masses, in particular of Coatings, floor coverings and adhesives.
CN110607159Arelates to hydrolysis-resistant polyester polyol, polyurethane prepared from the hydrolysis-resistant polyester polyol having acid value 0.1 to 1.0mgKOH/g, and the hydroxyl value 45 to 70mgKOH/g. obtained by reaction of castor oil, triethylene glycol, neopentyl glycol and adipic acid and no aromatic diacid or anyhydride, and application of the polyurethane in the field of adhesives..
FR1398390 discloses - a process for preparing a solvent based coating composition having excellent conservation of luster under the action of atmospheric factors comprising the reaction product of methylenebis(4-cyclohexyl isocyanate) (I) or its polyol addition compound and a fatty acid polyester (II). The II having an OH no. of 100-200 and an acid no. <12 is prepd. by a catalyst and solvent mediated method from polyols of mol. wt. 62-164 such as ethylene glycol; dibasic acids such as adipic and phthalic acid; and fatty acids such as oleic acid, as well as dimeric fatty acids and castor oil.
US4859735A discloses novel polyurethane formulations especially useful as membranes of the protection of bridge deckings prepared by mixing two components, A and B. Component A comprises castor oil modified with a ketone-formaldehyde condensate and also preferably contains an elastomer. Component B is a modified MDI, being a mixture of diphenylmethane diisocyanate and its reaction product with a low molecular weight poly(oxyalkylene).
WO2013012699A2 reveals a polyurethane based coating composition comprising a base and an activator wherein the base component comprises a polyol, a filler, a defoamer, a catalyst and a molecular sieve and the activator comprises polyisocyanate. Preferably the polyol comprises castor polyol, 2-methyl 1, 3 dipropanediol or 1, 4 butane diol and the filler comprises mica. The said coating composition is useful in coating concrete and metal surfaces.
Traversal of prior art reveals numerous polyester polyol, polyether polyol or modification of them to get successful one component or two component formulation for different applications. However very few reports are there for solvent free synthesis of polyol having low viscosity coupled with minor dependency on petroleum derived polyether polyol or elastomeric polyol. Thus there exists a need for the synthesis of solvent free polyester polyol having wide hydroxyl value range but low viscosity, negligible content of petroleum derived polyether polyol or elastomeric polyol and evaluation of the same as a two component coating system.

Objective of the invention
The primary objective of the present invention is to provide a polyester polyol having low viscosity involving long chain fatty oil or fatty acid having secondary hydroxyl group preferably 12-hydroxy-9-cis-octadecenoic acid by a solvent less method.
Another objective of the present invention is to provide said polyol polyester incorporating 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid wherein the content of the same would be more than 50% with respect to the weight of the polyester polyol.
Yet another objective of the present invention is to provide said polyol polyester wherein the usage of petroleum derived polyether polyol or elastomeric polyol should be less than 5%.
Still another objective of the present invention is to provide said polyol polyester which will be having wide range of hydroxyl value (75-300) and acid value <5.
Yet another objective of the present invention is to provide said polyol polyester which will be suitable for two component coating for brush or roller applications providing excellent hydrophobicity, chemical resistance and mechanical performance like tensile strength, elongation, chemical resistance, gloss etc. upon curing.
Another objective of the present invention is to provide said polyester polyol which would be especially useful as coating for car deck, bridge deck, waterproofing and construction purposes in addition to wood coating, industrial coatings etc.
Yet another objective of the present invention is to provide said solvent less method for the synthesis of the polyester polyol which would be free from catalyst and azeotropic distillation.

Summary of the Invention
Thus according to the basic aspect of the present invention there is provided 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols comprising
Polyester polyol as a reaction product of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid (55-85%), anhydrides/diacids and diol/polyols; wherein said diacids and/or anhydride is in select ratio of 0.1:1 to 0.7:1 with respect to hydroxy equivalent of said 12-hydroxy-9-cis-octadecenoic enriched fatty acid, said polyester polyol having hydroxyl value in the range of 100-280 mg KOH/g, acid value in the range of 0-20 mg KOH/g, and molecular weight (Mn) in the range of 400-2000 daltons.
Advantageously, said 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols is suitable for coating including wood coating, waterproofing membrane, cementitious waterproofing and floor coatings (car deck, bridge deck) including industrial coatings providing excellent hydrophobicity, chemical resistance and mechanical performance based on improved tensile strength, elongation, chemical resistance, gloss and are suitable for brush or roller or spray applications when thinned with solvent.
Preferably said 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols is provided that is solvent less flow-able polyester polyol wherein for desired tensile strength (1.0-11 Mpa) - % elongation (10-500%) balance, said anhydride/ diacids including aromatic/aliphatic anhydride/diacid involves at least one anhydride/diacid selected from phthalic anhydride, adipic acid, sebacic acid cyclohexane dicarboxylic acid (CHDA), tetrahydro phthalic acid, hexahydro phthalic acid or anhydride, maleic anhydride or combinations thereof, and,
wherein said diol/polyol includes both linear and branched alcohols as at least one diol selected from ethylene glycol, 1 ,2- propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,4-butanediol, 1 ,3-butanediol, 2,2- dimethyl-1 ,3-propanediol (= neopentyl glycol), 2,5-hexanediol, 1,6-hexandiol, 2,2-[bis- (4-hydroxy-cyclohexyl)]-propane, 1, 4-dimethylol cyclohexane, diethylene glycol and dipropylene glycol, and combinations thereof. whereas multi-functional alcohols include glycerol, hexanetriol, pentaerythritol, sorbitol, trimethylol ethane (TME), ditrimethylol propane, rimethylol propane (TMP) and combinations thereof, preferably NPG, HDO and TMP and combinations thereof; enabling said 12 hydroxy-9-cis-octadecenoic acid enriched polyester polyols having acid value preferably in the range of 0-5 mg KOH/g and molecular weight (Mn) preferably in the range of 500-1500 daltons.
According to another preferred aspect of the present invention there is provided said 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols wherein said polyester polyol is preferably a reaction product of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid 55-85%, Anhydride/Diacid 5-30%, and Diol/polyol 4-30%; favouring processable viscosity in the range of from 600 to 1200 poise at temperatures of 25 ?C for diverse coating formulations; and also allowing blending of said polyester polyols additionally with 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid for increased pot life free of any viscosity issues to require solvent dilution.
Preferably said 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols is provided wherein in said polyester polyol involvement of petroleum derived polyether polyol or elastomeric polyol is reduced from 10-25% to 0-2% and involvement of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid is maximized such as to enable said processable viscosity free of any solvent dilution, and also enables tensile strength (1.0-11 Mpa)/ elongation (10-500%) balance together with high hydrophobicity and good reactivity.
According to yet another preferred aspect of the present invention there is provided said 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols for incorporation in coating formulations either individually or as a combination of two different polyester polyol including ambient curing coatings, baked and thermoset coatings based on hardeners/ curing agents including polyisocyanates, urea-formaldehyde, melamine-formaldehyde wherein when the desired -OH value of said polyester polyol is 100-200 mg-KOH/g hardener for baking includes amino resin to favour thermoset coating, and wherein when the desired -OH value of said polyester polyol is 100-280 mg-KOH/g hardener for amino baking includes melamine formaldehyde resin and for PU includes Isocyanates (TDI, IPDI, HDI, polymeric MDI etc) and urea formaldehyde as curing agents.
According to another aspect of the present invention there is provided a process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols based on condensation polymerization free of any involvement of esterification catalyst and azeotrope solvent comprising the steps of
(i) Providing for reaction 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid (55-85%), anhydrides/diacids, and diol/polyols with said diacids or anhydride in select ratio of 0.1:1 to 0.7:1 in respect of hydroxy equivalent of said 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid; and
(ii) obtaining therefrom 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols having hydroxyl value 100-280 mg KOH/g and acid value 0-20 mg KOH/g with molecular weight (Mn) levels of 400- 2000 daltons.
Preferably in said process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols wherein said step (i) of providing 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid, anhydrides/diacids, and diol/polyols for reaction in said ratios and equivalents involves:
reacting by heating and refluxing at 170-185°C with continued heating till 220-230°C with constant removal of water of reaction by Dean-stark apparatus and after removal of 90% of water of reaction, monitoring acid value and viscosity of the resin every half an hour to reach to acid value in the range of 3-7 mg KOH/g and viscosity in the levels of 600-1200 poise at temperatures of 25 ?C, followed by cooling the batch to 100°C for discharge in a metal container thereby obtaining said low viscosity resin with excellent tensile strength and elongation.
According to yet another preferred aspect of the present invention there is provided a process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols wherein
said step (i) preferably involves 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid 55-85% along with at least one Anhydrides/Diacids 5-30%, and at least one Diol/polyols 4-30%, as reactants, for reacting under nitrogen providing to thereby obtain said 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols having hydroxyl value in the range of 100-280 mg KOH/g and acid value 0-20 mg KOH/g, molecular weight (Mn) 400- 2000 daltons and low processable viscosity in the range of from 600 to 1200 poise at temperatures of 25 ?C to favour diverse coating formulations.
Preferably in said process for the synthesis of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyols wherein followed to cooling the polyester polyol batch to 100°C for discharge in a metal container, the same is additionally blended with 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid to favour increase in pot life free of any viscosity issues and free of requiring any solvent dilution.
Detailed Description of the Invention
As discussed hereinbefore, the present invention provides for solvent less flow-able polyester polyol derived from high dosage of12-hydroxy-9-cis-octadecenoic acid enriched fatty acids for diverse two component curing applications exhibiting excellent hydrophobicity, chemical resistance and mechanical performance.
In the primary embodiment the present invention provides polyester polyol which is a 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid based polyester polyol derived from polymerization/polyesterification of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acids and low molecular weight glycols and at-least one aromatic/aliphatic diacids or anhydride wherein the amount of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acids ranges from 50-85%. The low molecular weight glycols are selected from aliphatic di or triols having primary/secondary hydroxyl group. The aromatic/aliphatic diacids or anhydride is used in a selective ratio from 0.1:1 to 0.7:1 with respect to the hydroxy equivalent of the 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid. The desired polyester polyol is having hydroxyl value 100-280 mg KOH/g and acid value 0-20 mg KOH/g, more preferably 0-5 mg KOH/g. Said 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid is "Fatty acids comprising 12-hydroxy-9-cis-octadecenoic acid (80-90%), Octadec-9-enoic acid (2-5%) and long chain alkanoic/alkenoic acid between 0.2-1% wherein Iodine value of 12-hydroxy-9-cis-octadecenoic acid is 82 to 89; Iodine value of Octadec-9-enoic acid is 85 to 95 and overall Iodine value of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid is 81 to 91.
The present advancement enabled synthesis of solvent free high 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid containing polyester polyol prepared by a process without using any azeotrope solvent and esterification catalyst having desired hydroxyl value and low viscosity where the usage of petroleum derived polyether polyol or elastomeric polyol is reduced from 10-25% to 0-2% and maximized involvement of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid was done to achieve hydroxyl value from 100-280 mg-KOH/g with easy process able viscosity. For the synthesis polyester polyol, majority of the prior arts have generated an acid terminated macro-monomer intermediate by stoichiometric excess of poly acids or anhydride followed by polyester synthesis involving said acid terminated macro-monomer with other glycols having high viscosity, which require solvent dilution during applications, whereas the present invention involves much less aliphatic/aromatic acid or anhydride and yet could successfully prepare polyester of hydroxyl value 100-280 mg-KOH/ with viscosity less than 1200 poise at temperature 25.?C without any solvent dilution.
The synthesized polyester polyol is useful as solvent less base for diverse coating systems. Reports are there wherein commercially available polyester polyols having very high OH value (250-300) are used to make final blend having lower hydroxyl value, such blends are generally useful for rigid foam applications but not for coating applications where high elongation and tensile strength both are important. It’s easy to make any blend of different -OH value but such low viscosity resin obtained completely by condensation reaction without requiring any blending and with excellent variability of tensile strength and elongation is not known. In addition, the present invention concerns polyol with high hydrophobicity and good reactivity that are obtainable by reacting 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid with aromatic/aliphatic diacid or anhydride followed by reaction with other multifunctional glycols to get final polyol of desired hydroxyl value.
In another embodiment the present invention provides polyester-polyol polymer having hydroxyl value 100-280 mg-KOH/g derived from 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid which can be used to prepare two component coating systems with improved properties (e.g. tensile strength, elongation, chemical resistance, gloss etc.) for brush or roller applications, optionally the resin can also be thinned with solvent for spray applications. The invented resin is especially useful as coating for car deck, bridge deck, waterproofing and construction purposes.
The resin can also be used for wood coating, industrial coatings etc. Optionally the resin can also be used for ambient acid cure coating where the hardener is urea-formaldehyde or melamine-formaldehyde where the desired hydroxyl value is from 100-150 mg-KOH/g. Optionally the resin with OH value 100-280 mg-KOH/g can also be used for baking with amino resin to make thermoset coating with preferred OH value 100-200 mg-KOH/g. Polyester of hydroxyl value 20-350 is known and also commercially available but such combination of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid with PA/TMP/NPG of such -OH value with tensile strength/elongation balance is not known.
In another embodiment, instead of single polyester, two different polyester of such 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid based formulation of different hydroxyl value can be used optionally for achieving versatility of tensile/elongation in final coatings. Out of the total 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid of 20-40% may optionally kept separated out of the polyester backbone and used as reactive diluent for making the base of the coating system.
In another embodiment in addition to exclusively technical requirement of the products, economic aspects play a major role of the current invention. In addition, there is an increasing focus on the overall eco-balance and environmental sustainability of commercial products.
The advancement according to the present invention is discussed in further detail in relation to the following non-limiting exemplary illustrations

Example- 1
Preparation of 12-hydroxy-9-cis-octadecenoic acid enriched polyester polyol:
In a 4 neck round bottom flask, 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid (procured as a packaged material from Maharashtra) together with other chemicals, phthalic anhydride, trimethylol propane, adipic acid, neopentyl glycol, triphenylphospite are added. The flask is attached with a mechanical stirrer, a thermometer, a nitrogen tube and a dean-stark condenser apparatus system. Heating is provided to the reactor and reflux starts at 170-185°C. Continue the heating of the batch till 220-230°C by constantly removing water of reaction by dean-stark apparatus. After removal of 90% of the theoretical water of reaction, acid value and viscosity of the resin are monitored in every half an hour. Once acid value is achieved 2-10 mg KOH/g, preferably 3-7 mg KOH/g, the batch is started to cool down to 100°C and discharged in a metal container.
Initial experiments for the synthesis of final polyester were carried out with dehydrated 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid as the major fatty acid source to prepare low viscous polyester polyol with high hydroxyl value (155 & 235). However, in those batches, pot life and tensile strength were found to be less when used in case of clear coat system and hence can be considered as a comparative for the Applicants present invention.
It was found by way of the present invention that polyester polyol as 100% resin product could be synthesized free of any involvement of esterification catalyst and free of any involvement of azeotrope solvent based on reacting 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid at 55-85% levels, at least one Anhydride/Diacids at 5-30% levels, and at least one Diol/polyol at 4-30% levels that obeys the diacids and/or anhydride: hydroxy equivalent of said 12-hydroxy-9-cis-octadecenoic enriched fatty acid ratio range of 0.1:1 to 0.7:1; to enable hydroxyl value in the range of 100-280 mg KOH/g, acid value in the range of 0-20 mg KOH/g, and molecular weight (Mn) in the range of 400-2000 daltons, favouring processable viscosity in the range of from 600 to 1200 poise at temperatures of 25 ?C suitable for diverse coating formulations. The reaction can successfully proceed based on one single diacid and one single diol when the above ratio and the wt.% ranges are obeyed to give the desired polyester polyol free of any solvents and having the desired attributes as stated above that is thus in accordance with the present invention.
An exemplary non-limiting reactor charge leading to a polyester polyol of the present invention is presented below.
TABLE 1:
REACTOR CHARGE
12-hydroxy-9-cis-octadecenoic acid enriched fatty acid 85 55
Phthalic anhydride 9 20
Adipic Acid
Neopentyl glycol 0
Trimethylol propane 6 25
Total 100 100
Final Hydroxyl Value 172 280
Ratio of Anhydride or acid equivalent/ Fatty acid -OH equivalent 0.27 0.69

In another embodiment of the present invention the desired polyester polyol was achieved involving select levels of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid, wherein maximum levels of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid in the formulation to manage viscosity was involved, beyond which levels though can be incorporated but required tensile strength and elongation balance with maximum pot life could not be achieved. The requirement was solvent free system of polyester polyol but flowable, thus monomers were selective to give lower Tg and viscosity of the final polyester, wherein the monomers involved 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid, aromatic/aliphatic anhydride/diacid including phthalic anhydride, adipic acid and diol/polyols includes but not limited to, trimethylol propane, neopentyl glycol in select amounts.
In another preferred embodiment of the present invention from the total content of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid around 20-40% was optionally kept separated out of the polyester backbone and used as reactive diluent for making the base of the coating system, and solvent is avoided for processing. Addition of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid with the synthesized polyester polyol advantageously favored increased pot life of 20 to 30 minutes with respect to same quantity of isocyanate as curing agent.
In another embodiment of the present invention to avoid negative impact on pot life of the final polyurethane no catalyst including Tin based esterification catalyst was employed for the synthesis of the polyester polyol. Select reagents with select quantities without any azeotropic solvent under selective reaction condition provided the very high hydroxyl containing polyester polyols of the present invention.
Thus the present invention provides polyester polyol having hydroxyl value 100-280 mg-KOH/g and acid value 0-20 mg KOH/g, more preferably 0-5 mg KOH/g having molecular weight (Mn) not more than 2000 daltons, more preferably 500-1500 daltons derived from 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid. Said polyol is obtained by reacting 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid (50-85%) with aromatic/aliphatic anhydride or acid in presence of other multifunctional glycols wherein the ratio between anhydride/acids and hydroxy-equivalent of fatty acid is from 0.1:1 to 0.7:1.

Present invention also attains synthesis of solvent less flow-able Polyester polyol by a condensation polymerization process without using any azeotrope solvent and esterification catalyst producing said polyester polyol with low viscosity (less than 1200 poise at 25 ?C) with excellent tensile strength and elongation where the usage of petroleum derived polyether polyol or elastomeric polyol was reduced from 10-25% to 0-2% employing much lesser aliphatic/aromatic acid or anhydride.

Said Polyester polyol having High hydrophobicity and good reactivity can be used for diverse two component curing applications such as coating for car deck, bridge deck, waterproofing and construction purposes. The resin of the present invention as scoped can also be used for wood coating, industrial coatings etc. with excellent hydrophobicity, chemical resistance and mechanical performance. (e.g. tensile strength, elongation, chemical resistance, gloss etc.) and suitable for brush or roller application and spray applications while thinned with solvent.

Thus present invention enables successful manufacture of solvent less flow-able polyester polyol derived from high dosage of 12-hydroxy-9-cis-octadecenoic acid enriched fatty acid, as low viscosity 100% product resin free of solvents through condensation with excellent tensile strength and elongation. Said composition can be used for diverse two component curing applications exhibiting excellent hydrophobicity, chemical resistance and mechanical performance.