Claims:We Claim:
1. Enzymatically trans-esterified and hydrolyzed Oil (ETHO) comprising enzymatically trans-esterified and hydrolyzed oil (ETHO) which is 100% sugar alcohol trans-esterified oil, adapted for alkyds.
2. Enzymatically trans-esterified and hydrolyzed Oil (ETHO) as claimed in claim 1 wherein said trans-esterified and hydrolyzed Oil (ETHO) includes refined/ raw oil and drying / non-drying oil with iodine value in the range of 5-200 gm I2 / 100 gm is present at the levels of 55-85 wt%, and, sorbitol (70% solution in water) in the levels of 10-20 wt%.
3. Enzymatically trans-esterified and hydrolyzed Oil (ETHO) as claimed in claims 1 or 2 wherein said enzymatically trans-esterified and hydrolyzed Oil (ETHO) have glyceride and free fatty acid distribution of: monoglycerides 11-32%, diglycerides 22-27%, triglycerides 8-28%, and free fatty acid 30-50% with minimum 1: 1.75-2 tolerance of solvent mix of Methanol: Ethanol:: 10:3 by volume and acid value of 60-90 (mg KOH /gm), that is further processable and storage stable for 1 month at ambient temperature of 20-35°C, and is adapted for alkyds that are both air drying and force drying type.
4. Enzymatically trans-esterified and hydrolyzed Oil (ETHO) as claimed in claims 1-3 wherein said sugar alcohol trans-esterified and hydrolyzed Oil (ETHO) includes sorbitol, sucrose trans-esterified oil; said oil includes vegetable oil selected from refined/ raw oil and non-drying oil including soyabean oil, linseed oil, Palmolein Oil; and said solvent is selected from water and tert-butanol.
5. A process for the preparation of enzymatically trans-esterified and hydrolyzed Oil (ETHO) as claimed in claims 1-4 comprising the steps of
Providing alkali refined/ raw oil and non-drying oil, sugar alcohol and enzyme for reaction with or without solvent and heating the reaction mass at low temperature of 40-80°C preferably 70±2°C that is maintained for 8-10 hrs at 70°C and 14-16 hrs at ambient temp of 22-30°C during a 24 hrs cycle;
Continuing the reaction for 72 hrs until ETHO formed showed minimum 1: 1.75-2 tolerance with solvent mix of Methanol: Ethanol : : 10:3 by volume and acid value of min 60 (mg KOH /gm) followed by cooling to ambient temperature, filtering and packing to thereby obtain a storage stable ETHO adapted for alkyd synthesis.
6. A process for the preparation of enzymatically trans-esterified and hydrolyzed Oil (ETHO) as claimed in claim 5 wherein said sugar alcohol is preferably sorbitol (70% solution in water); enzymes are selected from Novozym 435, Lipozyme RM IM , that are recyclable to provide desired efficacy; said solvent is preferably, water.
7. Sugar alcohol based alkyds comprising reaction product of
trans-esterified and hydrolyzed oil (ETHO) that is 100% sugar alcohol trans-esterified oil as claimed in claims 1-4,
at least one polyol selected from sugar alcohol, glycerine; and
polybasic, and optionally, monobasic acids.
8. Sugar alcohol based alkyds as claimed in claim 7 wherein
Said trans-esterified and hydrolyzed oil (ETHO) that is 100% sugar alcohol trans-esterified oil based on refined/ raw oil and non-drying oil is present in the levels of 60-65 wt.%;
Said at least one polyol selected from sugar alcohol, glycerine is present in the levels of 5-15 wt.%;
Said polybasic, and optionally, monobasic acids is present in the levels of 18-35 wt.% adapted for clear alkyds that are both air drying and force drying types.
9. Sugar alcohol based alkyds as claimed in claims 7-8 wherein said force drying type alkyd is obtained as clear non-drying oil alkyd resin solution preferably at 50-60% in xylene for curing with amino resin cross-linker preferably melamine formaldehyde resin; and
wherein said clear air drying alkyd is based on refined/ raw semi drying/ drying oil adapted for auto oxidative curing in presence of metallic driers.
10. A process for the preparation of sugar alcohol based alkyds as claimed in claims 7 comprising the steps of
involving enzymatically trans esterified and hydrolyzed Oil (ETHO) based on refined/ raw oil and non-drying oil, phthalic anhydride optionally benzoic acid, with at least one polyol selected from sugar alcohol, glycerine with or without catalyst preferably dibutyl tin oxide in solvents preferably xylene/ methyl amyl ketone as reflux solvents to provide for a reaction mixture;
heating the reaction mixture initially to 170°C to take out water of sugar alcohol preferably sorbitol followed by raising the reaction temperature slowly to 200-210°C until clear solution is obtained;
increasing further the reaction temperature to 230-240°C and maintained for 6-12 hrs to obtain an acid value of the reaction mix in the range of 5-25 mg KOH/gm and after processable viscosity is achieved terminating the reaction to obtain therefrom said sugar alcohol based alkyds.
11. A process for the preparation of sugar alcohol based alkyds as claimed in claim 10 that is diluted with mineral turpentine oil, cooled to <120°C, filtered and packed as storage stable alkyds established through accelerated stability test at 55°C for 30 days with no appreciable change in the viscosity, and is adapted for air drying clear coating compositions based on metallic driers comparable to conventional alkyds.

Dated this the 18th day of March, 2021 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
IN/PA-199

, Description:FIELD OF THE INVENTION
The present invention provides for enzymatically trans-esterified and hydrolyzed Oil (ETHO) and an alkyd thereof involving low cost sorbitol/carbohydrates/other polyols with said alkyds preferably involving 100% sorbitol as the polyol, suitable for surface coating applications. An enzymatic process to synthesize said ETHO and further the alkyds based on vegetable oils & polyols is also provided to reach to alkyds having desired oil length, molecular weight and end use in respect of surface coating applications.
BACKGROUND ART
Vegetable oils (triglycerides of fatty acids) or their fatty acids are the major component of oil modified polyesters. Presently vegetable oil based alkyds are commercially synthesized through transesterification reaction of an Oil with Polyols at elevated temperature of 240-260°C in presence of suitable metal salts/oxides as catalyst. This provides corresponding monoglycerides and diglycerides of the polyol resulting in reactive sites and compatibility for further reaction with polybasic acids. This process holds good for most of the polyols but not for Sorbitol and other carbohydrates as being the preferred low cost bio based sugar alcohol. This can be attributed to the fact that sorbitol undergoes dehydration and cyclization yielding sorbitan and isosorbide at transesterification reaction temperature of 230–250°C thereby consuming primary alcohols resulting in reduced functionality and therefore poor transesterification reaction of vegetable oil and sorbitol in the first step does not allow further esterification reaction involving polyol and polybasic/monobasic acids to obtain an alkyd resin. Secondly, dark brown color of reaction mass due to charring of sorbitol / carbohydrate at elevated transesterification reaction temperature. Presently there is no process to address these issues associated with use of sorbitol.
References are invited to US20120065419A1- disclosing methods of producing ricinoleic acid ester by selective enzymatic transesterification of mixed or pure vegetable oil particularly castor oil with light alcohols.
US 4416991 teaches method for enzymatic transesterification of lipid and enzyme used therein with continuously or repeatedly contacting enzyme or preparation of enzyme which have transesterification activity with fats or oils.

US2006257982A1 relates to methods for producing fats or oils through improving the productivity of enzymatic transesterification or interesterification by purifying the substrate oil.
US2010151079A1 teaches about the possible synthesis of margarine oil produced by enzymatic interesterification of the mixed fatty acid / esters different from hydrogenated oil and have low palmitic acid content.
Alkyd resin synthesis by enzymatic alcoholysis by Renata Kobal Campos de Carvalho, Fernando dos Santos Ortega, Andreia de Araujo Morandim Giannetti, in Iranian Polymer Journal volume 28, pages747–757(2019) teaches synthesized alkyd through transesterification of vegetable oil with glycerine at different stoichiometry in presence of Novozym 435. It was established that glycerin/vegetable oil ratio of 1:3.5 (mol/mol) at 56.73°C and 9.36% enzyme concentration based on Oil’s mass (W/W) yielded best results of transesterification. Authors subsequently formed alkyd by reacting with phthalic anhydride.
Enzymatic production of alkyl esters through alcoholysis: A critical evaluation of lipases and alcohols- Li deng et al, Journal of the American Oil Chemists' Society volume 82, pages341–347(2005) and the researches therein evaluated the commercially available immobilized lipase enzymes for transesterification of sunflower oil with monohydric alcohols where Novozym 435 yielded over 90% alkyl esters.
Enzymatic Synthesis of Medium Chain Monoglycerides in a Solvent-Free System by Marta A. P. Langone, L Melissa E. De Abreu, 2 Michelle J. C. Rezende, 2 And Geraldo L. Sant' Anna, Jr., Applied Biochemistry and Biotechnology, Vols. 98-100,2002 synthesized monocaprin, monolaurin, and monomyristin from fatty acids and glycerols using 9% of commercially immobilized lipase. The reaction was carried out in solvent free medium at 60°C for about 5-6 hours in simple batch reactor. Almost 80% conversion to monoglycerides was achieved. Monoglycerides obtained were about twice the quantity of diglycerides and triglycerides were formed in traces.
Enzymatic synthesis of carbohydrate esters of fatty acid (I) esterification of sucrose, glucose, fructose and sorbitol by Hajime Seino, Tsuyoshi Uchibori, Toshiyuki Nishitani & Sachiko Inamasu, Journal of the American Oil Chemists’ Society volume 61, pages1761–1765, 1984- attempted to synthesize the carbohydrate esters of fatty acid and carbohydrates like sucrose, glucose, fructose and sorbitol using lipase enzyme. The reaction was performed in the buffer solution at 40°C.
Enzymatic Synthesis of Monoglycerides by Lipase-Catalyzed Glycerolysis by Hu Sun Wan Peng Wang Fang Deng Li, Beijing University of Chemical Technology, Department of Bioengineering, Beijing 100029, studied effect of solvent and enzyme dosage on synthesis of lipase catalyzed Glycerolysis of soya oil, salad oil and palm oil with glycerol. Author claimed that maximum conversion to 74.04% of monoglycerides is achieved at 46°C using 4% water, Lipozyme TLIM 0.1-2 g, glycerol to palm oil ratio of 3.7:1 for 30 hours.
Enzyme catalysts in polymer chemistry By Vlcek, Tomas Edited By: Kalendova, Andrea From Sbornik Prispevku - Mezinarodni Konference o Naterovych Hmotach, 38th, Sec, Czech Republic, May 21-23, 2007 (2007), 226-230 includes references on Lipase types of enzymes that are becoming a new class of catalysts applicable in polymer chemistry. They can efficiently catalyze polycondensation, (trans)esterification, "ring-opening", and oxidation reactions. Therefore, they are highly perspective namely in production of polyester resins, alkyd resins, polyamides, and epoxidized oils. Lipases are regarded as environmentally friendly catalysts that improve efficiency and selectivity of chemical reactions, and compared to conventional catalysts significantly lower energy demands of polymers production.
Use of Vegetable oil and sorbitol/ other sugars while has provided a unique solution for alkyd synthesis but could not be made possible in conventional ways of alkyd synthesis as the enzymes used are in higher amounts and alkyds were generated with monogyceride content of 40-65% of conventional/ enzymatic alkyds based on alcoholysis.
A comparative study on coating properties of chemoenzymatically synthesized and conventional alkyd resins By Athawale, V. D.; Joshi, K. R. From Paintindia (2001), 51(3), 47-50 relates to chemoenzymatic synthesis of alkyd resins based on modified castor oil. The processes involved in the synthesis are: (1) Lipase catalyzed interesterification of castor oil and linseed oil at near ambient temperature to form an interesterification product and (2) Esterification with phthalic anhydride. The article also describes the comparison of coating properties of the newly synthesized alkyd resins with those prepared by the conventional method. The various coating properties determined were hardness, adhesion, impact resistance, storage stability, chemical resistance and color. Overall, chemoenzymatically synthesized alkyd resins showed better coating properties than the commercially available alkyd resins. This prior literature does not enable the use of sorbitol as polyol in combination with lower cost Soya bean oil and other similar semi drying oils with select iodine value of 120-145, to provide for an alkyd but instead teaches the involvement of castor oil/ modified castor oil/ linseed oil.
Chemoenzymatic synthesis of oil-modified acrylic monomers as reactive diluents for high solid coatings By Bhabhe, M. D.; Athawale, V. D. From Progress in Organic Coatings (1997), 30(4), 207-211 teaches an approach for achieving high solid coating through the use of a reactive diluent in the system. In this prior study, the chemoenzymatic synthesis of oil modified acrylic monomers has been reported. The diglyceride separated by column chromatographic from partial esters synthesized by lipase-catalyzed transesterification of soybean and linseed oil with n-butanol (Step I) was further subjected to acryloylation or methacryloylation to yield oil-modified acrylate or methacrylate monomer, resp. The newly synthesized monomers were characterized by IR, 1H NMR, solubility, resin compatibility and their evaluation as reactive diluents in high solid coating compositions. This prior art deals with the diglycerides obtained from enzymatic transesterification of Soyabean Oil and linseed oil. Diglycerides were isolated from the reaction mass and subjected to acryloylation or methacryloylation to yield oil-modified acrylate or methacrylate monomers. Such acrylates have been used as reactive diluents and is an entirely different molecule/ approach than subject invention disclosure dedicated for the pure alkyd synthesis.
Synthesis of alkyds involving regioselective lipase-catalyzed transesterification in organic media By Kumar, G. Sudesh; Ghogare, A.; Mukesh, D. From Journal of Applied Polymer Science (1997), 63(1), 35-45 again teaches porcine pancreatic lipase that is established as an effective biocatalyst for the selective transesterification of triglycerides and diols in organic medium at room temperature yielding primarily 2-monoglyceride mixtures. Molecular modeling simulations of repeating units of alkyd resin incorporating one- and two-monoglycerides show end-to-end distance of 9.76 and 12.82 Å, resp. The modeling studies on the trimers of these repeating units also reveal more extended configuration for the structures based on two-monoglycerides. A comparative study of alcoholysis by conventional base-catalyzed process and this novel biocatalytic process was carried out with coconut oil triglycerides and a series of diols, followed by polymerization. The rates of transesterification were dependent on the nature of triglyceride, diol, concentration of the enzyme, and temperature. The 1, 3 specificity of lipase produced 2-monoglycerides as determined by periodic acid method, resulting in uniform distribution of fatty acids along the alkyd polyester backbone. Comparisons are made between those alkyds prepared by base catalysis and biocatalytic method. This prior art specifically employs non-drying coconut Oil and diols meant for low mol. wt. alkyds which may possibly find usage with amino resin or isocyanate crosslinkers.
Enzymic synthesis of alkyds By Geresh, Shimona; Gilboa, Yigal From Biotechnology and Bioengineering (1990), 36(3), 270-4 teaches lipases used as catalysts in the synthesis of all-trans polyester oligomers in organic solvents. Esters of fumaric acid and 1, 4-butanediol served as the substrates in the enzyme-catalyzed polytransesterification. No isomerization of the double bond was found under the mild conditions of enzymic catalysis used, as opposed to the extensive isomerization found during chemical polycondensation. The alkoxy leaving group of the ester fumarate was found to be responsible for the rate of transesterification. Low (Mw = 600-800) and high (Mw = 1250) mol. wt. alkyds were synthesized depending on whether THF or acetonitrile, resp., was used as the solvent. Here ester fumarates have been used to synthesize very low MW resins and does not include the disclosure for alkyds meant for surface coatings.
Process for the preparation of alkyd resins By Lapis, Alexandre Augusto Moreira; Petzhold, Cesar Liberato; Libio, Illen Canani; Barrios, Silmar Balsamo From Braz. Pedido PI (2015), BR 2008023493 A2 20151027 teaches preparation of alkyd resins by a transesterification process through enzymatic catalysis, using mild condition, with maximum temperatures of 90°C.
Process for preparing alkyd resins, urethanized alkyds and urethane oils By Vlcek, Tomas; Kuncova, Gabriela; Sabata, Stanislav; Hetflejs, Jir From Czech Rep. (2013), CZ303842B6 20130522 teaches a process for preparing alkyd resins and/or urethanized alkyds and/or urethane based on vegetable and/or animal oils being carried out in three stages wherein the preparation process is characterized in that in the first stage, there is carried out alcoholysis consisting in transesterification of vegetable and/or animal oils and/or fatty acids and/or fatty acid alkyl esters of vegetable and/or animal oils, wherein the alcoholysis is carried out at a temperature ranging from 40 to 70°C and in the presence of enzymatic catalysts. In the second stage, there is carried out polycondensation of alcoholyzate with monocarboxylic and/or polycarboxylic acids and/or with monoalcohols and/or with polyalcohols. In the third stage, there is carried out an addition reaction comprising adding to the alcoholysis and polycondensation products an arbitrary type of isocyanate and subsequently monoalcohol. For the preparation of urethane oils, the first stage and the third stage of the above-described process are carried out. Claim 1 therein teaches process for the preparation of alkyd resins and / or urethanized alkyds and/ or urethane oils based on vegetable and / or animal oils, carried out in two or more stages, characterized in that the first stage is carried out at 40 to 70°C for the presence of enzymatic catalysts consisting of the transesterification of vegetable and / or animal oils and / or fatty acids and / or alkyl esters of fatty acids of vegetable and / or animal oils, in a second step polycondensation of the alcoholysate with monocarboxylic and / or polycarboxylic acids and / or monoalcohols; and / or with polyalcohols, in the third step, an addition reaction is carried out wherein any type of isocyanate is added to the alcoholysis and polycondensation product followed by the monoalcohol, the first step and the third step of the above process being carried out to prepare urethane oils. Under the Detailed Description of the Invention teaches as the “first step being the so-called alcoholysis, which consists in the transesterification of vegetable and / or animal oils and / or fatty acids and / or alkyl esters of vegetable and / or fatty acids animal oils with low molecular weight polyols. Vegetable oils are most often soy, linseed or rapeseed oil with a high content of unsaturated fatty acids. Low molecular weight polyols are most commonly pentaerythritol, glycerol, trimethylolpropane and sorbitol. The resulting product of the first phase is the so-called alcoholysate. In the next phase, the polycondensation is initiated with the addition of mono- or polycarboxylic acid. While this prior art teaches about alcoholysis with other polyols but not with sorbitol/ sugars having higher content of secondary hydroxyls.
Reference is made to renewable materials in surface coatings By Haseebuddin, Syed; Patil, Nitin V. From Paintindia (2006), 56(12), 81-82, 84-86. Teaches maturing of conventional technologies, depletion in petroleum based resources and their long-term effect on environment is driving scientists to seek new paradigms based on biol. concepts and renewable materials. This prior study discusses the possible potential uses of natural resources in surface coatings. Novel raw materials such as oils (Mahua, Vernonia, Lesquerella etc), polyols (Inulin and sucrose), additives (Isosorbide), enzymes (Porcine Pancreatic Lipase and Candida cylindracaea, Lipozyme), bio-mimetic catalysts (Iron-ascorbic acid palmitate) etc have been suggested for use in coatings. All these raw materials are from undepletable renewable resources, which are increasingly desirable in coatings technology. This article specifically teaches renewable materials used in coatings and does not specifically mentions about enzymatic synthesis of alkyds.
Process for enzymic preparation of monoglycerides suitable for conversion to alkyd resins By Kumar, Gajulapalli Sudesh; Ghogare, Ashok Dynandev From Indian (1992), IN 170642 A1 19920425 is found to teach a process of transesterification at 30-80° of predetermined amounts of a triglyceride-containing vegetable oil with an alcohol in the presence of lipase as catalyst, the reaction being effected in a nonaqueous organic solvent. Triglyceride-containing vegetable oils include safflower oil, tobacco seed oil, castor oil, coconut oil, linseed oil, rice bran oil and soybean oil. The alcohol is selected from monofunctional alcohols such as 2-butoxyethanol, diols such as 1, 4-cyclohexanedimethanol (I), and polyols such as trimethylolpropane. Transesterification of 0.11 mol coconut oil with 0.35 mol (I) in 30 g THF containing 15 g porcine pancreatic lipase at 30° for 3 days resulted in 100% conversion to 100% monoglycerides, compared with 74.19% monoglycerides and 25.8% diglycerides at 240° in xylene using Ca(OAc)2 as catalyst. This prior art employs most of the polyols except sorbitol/ carbohydrate sugars.
KR101188971B1 teaches high functional, highly branched or hyperbranched polyesters based on dipolycarboxylic acids, tricarboxylic acids or polycarboxylic acids, and diols, triols, polyols and relates to the process for producing the polyester, and to the use thereof. Under the DESCRIPTION section teaches “R. A. Gross and co-workers describe the synthesis of branched polyesters by reaction of dicarboxylic acids with glycerol or sorbitol and aliphatic diols. This synthesis is carried out by enzymatic catalysis and leads to “soft” products with glass transition temperatures of -28 ° C to 7 ° C: Polymer Preparation 2003, 44 (2), 63 (5), Macromolecules 2003, 36, 8219 and Macromolecules 2003, 36, 9804. The reaction involves an enzyme catalyzed reaction and generally has a long reaction time, which significantly reduces the space/ time yield of the reaction and increases the production cost of the polyester. In addition, only certain monomers such as adipic acid, succinic acid, glycerol, sorbitol or octanediol can react with the enzyme, while products such as phthalic acid, trimethylolpropane or cyclohexanediol are catalyzed to induce a reaction. This prior art primarily teaches about synthesis of oil free polyesters and does not require transesterification / hydrolysis of vegetable oil which is the basic requirement of the present invention.
It is thus apparent from the state of prior art teachings that while several enzyme based processes even moderate temperature processes are known there is a requirement in the art to explore for low cost bio based sorbitol / carbohydrates / other Polyols towards synthesis of Alkyds and to achieve compatibility with polybasic acids for subsequent esterification and polymerization to the extent to attain compatibility by not allowing much monoglyceride formation while using sorbitol to thereby not only enable compatibility/reactive sites for further reaction with polybasic acid to arrive at desired alkyd resin by completion of reactions, and in the process would also eliminate the use of metal oxides and high temperatures to also allow 100% sorbitol based alkyd which is difficult to attain through conventional transesterification processes.
Currently, also there is no process available which allows monoglyceride/ transesterification involving vegetable oils and sorbitol in the first as well as second step of alkyd synthesis thereby enabling synthesis of alkyds having low cost bio based sorbitol or similar sugar alcohols as sole polyol or 100% of polyol component, therefore been a subject of great interest to develop an alkyd synthesis route involving vegetable Oils and 100% sorbitol or like of the polyol component.
OBJECTS OF THE INVENTION
Thus the primary object of the present invention is to provide for enzymatically trans-esterified and hydrolyzed Oil (ETHO) and alkyds thereof involving low cost bio based sorbitol/carbohydrates/other polyols and alkyds preferably involving 100% sorbitol as the polyol, suitable for surface coating applications.
Another object of the present invention is to provide for low cost bio based sorbitol/ carbohydrates/ other polyol based alkyds involving sorbitol/ sugars having higher content of secondary hydroxyls and having low monoglyceride content of about 18-25% and enabling compatibility/ reactive sites for further reaction with polybasic acid to arrive at desired alkyd resin by completion of reactions.
Yet another object of the present invention is to provide for low cost bio based sorbitol/ carbohydrates/ other polyol based alkyds by way of a process by carrying out transesterification of vegetable oils with said polyols as well as hydrolysis of vegetable oil to achieve compatibility with polybasic acid for subsequent esterification and polymerization to reach to the desired alkyd.
Another object of the present invention is to eliminate use of metal salt/ oxides as employed in conventional process of transesterification of Oils and polyols in the first step of alkyd synthesis and such that the reaction may be conducted at low temperature of 45-70?C instead of the conventionally used 240-260°C as the use of catalyst/ high temp results in dehydration/ charring of sorbitol and consequently loss of sorbitol as a reactive ingredient.
It is another object of the present invention to provide for an approach to make low cost sorbitol usable in the process of synthesis of the alkyd that does not allow monoglyceride formation with sorbitol employing conventional process.

SUMMARY OF THE INVENTION
Enzymatically trans-esterified and hydrolyzed Oil (ETHO) obtained from vegetable Oils and polyols and a low cost alkyd obtained thereof for preparing Enamels and Primers is provided.
According to a basic aspect of the present invention there is provided enzymatically trans-esterified and hydrolyzed Oil (ETHO) comprising enzymatically trans-esterified and hydrolyzed oil (ETHO) which is 100% sugar alcohol trans-esterified oil, adapted for alkyds.
Preferably in said enzymatically trans-esterified and hydrolyzed Oil (ETHO) said trans-esterified and hydrolyzed Oil (ETHO) includes refined/ raw oil and drying / non-drying oil with iodine value in the range of 5-200 gm I2 / 100 gm that is present at the levels of 55-85 wt%, and, sorbitol (70% solution in water) in the levels of 10-20 wt%.
According to a preferred aspect of the present invention there is provided said enzymatically trans-esterified and hydrolyzed Oil (ETHO) wherein said enzymatically trans-esterified and hydrolyzed Oil (ETHO) has glyceride and free fatty acid distribution of: monoglycerides 11-32%, diglycerides 22-27%, triglycerides 8-28%, and free fatty acid 30-50% with minimum 1: 1.75-2 tolerance of solvent mix of Methanol: Ethanol:: 10:3 by volume and acid value of 60-90 (mg KOH /gm), that is further processable and storage stable for 1 month at ambient temperature of 20-35°C, and is adapted for alkyds that are both air drying and force drying type.
Preferably in said enzymatically trans-esterified and hydrolyzed Oil (ETHO) wherein said sugar alcohol trans-esterified and hydrolyzed Oil (ETHO) includes sorbitol, sucrose trans-esterified oil; said oil includes vegetable oil selected from refined/ raw semi drying /drying oil and non-drying oil including soyabean oil, linseed oil, Palmolein Oil; and said solvent is selected from water and tert-butanol.
According to a preferred aspect of the present invention there is provided a process for the preparation of enzymatically trans-esterified and hydrolyzed Oil (ETHO) comprising the steps of
Providing alkali refined/ raw oil and non-drying oil, sugar alcohol and enzyme for reaction with or without solvent and heating the reaction mass at low temperature of 40-80°C preferably 70±2°C that is maintained for 8-10 hrs at 70°C and 14-16 hrs at ambient temp of 22-30°C during a 24 hrs cycle;
Continuing the reaction for 72 hrs until ETHO formed showed minimum 1: 1.75-2 tolerance with solvent mix of Methanol: Ethanol : : 10:3 by volume and acid value of min 60 (mg KOH /gm) followed by cooling to ambient temperature, filtering and packing to thereby obtain a storage stable ETHO adapted for alkyd synthesis.
Preferably in said process for the preparation of enzymatically trans-esterified and hydrolyzed Oil (ETHO) said sugar alcohol is preferably sorbitol (70% solution in water); enzymes are selected from Novozym 435, Lipozyme RM, Lipozyme TLIM, Novozym 51003, Novozym BAN 480 LS that are recyclable to provide desired efficacy; said solvent is preferably tert-butanol, water.
According to another aspect of the present invention there is provided sugar alcohol based alkyds comprising reaction product of
Said trans-esterified and hydrolyzed oil (ETHO) that is 100% sugar alcohol trans-esterified oil,
at least one polyol selected from sugar alcohol, glycerine; and
polybasic, and optionally, monobasic acids.
Preferably, in said sugar alcohol based alkyds wherein
Said trans-esterified and hydrolyzed oil (ETHO) that is 100% sugar alcohol trans-esterified oil based on refined/ raw semi drying /drying oil and non-drying oil is present in the levels of 60-65 wt.%;
Said at least one polyol selected from sugar alcohol, glycerine is present in the levels of 5-15 wt.%;
Said polybasic, and optionally, monobasic acids is present in the levels of 18-35 wt.% adapted for clear alkyds that are both air drying and force drying types.

Preferably sugar alcohol based alkyds is provided wherein said force drying type alkyd is obtained of clear non-drying alkyd based on non-drying oil having 50-60% Resin solids and required viscosity for curing with amino resin cross-linker preferably melamine formaldehyde resin; and wherein said clear air drying alkyd is based on refined/ raw oil adapted for curing with metallic driers.
According to another preferred aspect of the present invention there is provided a process for the preparation of sugar alcohol based alkyds comprising the steps of
involving enzymatically trans esterified & hydrolyzed Oil (ETHO) based on refined/ raw oil and non-drying oil, phthalic anhydride optionally benzoic acid, with at least one polyol selected from sugar alcohol, glycerine with or without catalyst preferably dibutyl tin oxide in solvents preferably xylene/ methyl amyl ketone as reflux solvents to provide for a reaction mixture;
heating the reaction mixture initially to 170°C to take out water of sugar alcohol preferably sorbitol followed by raising the reaction temperature slowly to 200-210°C until clear solution is obtained. Reaction temperature is further raised to 230-240°C and maintained for 6-12 hrs to obtain an acid value of the reaction mass in the range of 5-25 mg KOH/gm and viscosity as mentioned in the examples and terminating the reaction to obtain therefrom said sugar alcohol based alkyds.
Preferably in said process for the preparation of sugar alcohol based alkyds the same is diluted with mineral turpentine oil, cooled to <120°C, filtered and packed as storage stable alkyds established through accelerated stability test at 55°C for 30 days with no appreciable change in the viscosity, and is adapted for air drying clear coating compositions based on metallic driers comparable to conventional alkyds.

DETAILED DESCRIPTION OF THE INVENTION
As discussed hereinbefore, the present invention provides for enzymatically trans-esterified and hydrolyzed Oil (ETHO) and alkyds thereof involving low cost bio based sorbitol/carbohydrates/other polyols and alkyds even involving 100% sorbitol as the lone polyol, which sorbitol has higher content of secondary hydroxyls and such that the alkyd attained has low monoglyceride content of about 18-25% thereby enabling compatibility/ reactive sites for further reaction with polybasic acid to favour the desired alkyd resin by completion of reactions.
Present invention relates to the development of a novel approach to prepare enzymatically trans-esterified and hydrolyzed Oil (ETHO) and alkyds thereof or oil modified polyesters employing vegetable oil and sugar alcohol preferably sorbitol as starting material in presence of enzyme enabling trans esterification/ hydrolysis at low temperature of 40-80°C. This provides monoglyceride, diglyceride and corresponding fatty acid as precursor for further reaction with suitable polybasic acid to synthesize alkyds having desired oil length, molecular weight and end use in respect of surface coating applications.
Preferably, the present invention involves synthesis of alkyds through enzymatic transesterification/ hydrolysis of vegetable oils with sugar alcohols as polyols/ carbohydrates like sorbitol, sucrose as one of the polyol in combination with conventional Polyols.
In the present invention, alkyd Resins have been synthesized involving i) enzymatic transesterification / hydrolysis of Vegetable oil and Sugar Alcohols e.g. Sorbitol or like in an aqueous medium at low temp of 40–80°C ii) Reaction mass thus obtained was further reacted at an elevated temperature of 200-250°C with additional quantity of sugar alcohols and dicarboxylic acid anhydride / monocarboxylic acid as per desired oil length of the alkyd
In the present invention sorbitol (70% aqueous solution) has been selected as sugar alcohol as it being the cheapest polyol available. Aqueous solution of sorbitol provides ease of transportation /storage / handling/ use as it being hygroscopic in nature. Presence of water provides aqueous reaction medium facilitating partial hydrolysis of Oils and compatibility with dibasic/ monobasic acids necessary for esterification reaction to get an alkyd.
Only Castor Oil is an exception here and not in the scope of the present invention as 90% of it being a triglyceride of hydroxy functional Ricinoleic acid, it acts as a fatty acid and does not require monoglyceride in the first step with respective polyol to compatibilize with polybasic / monobasic acid for further esterification reaction.
In the present invention enzymatic transesterification / hydrolysis has been carried out in an organic solvent free aqueous medium in the first step followed by esterification reaction at elevated temperature involving rest of the sorbitol and polybasic /monobasic acids using methyl amyl ketone as reflux solvent in place of conventionally used xylene and free from any esterification catalyst thereby making it a clean and green process of alkyd synthesis.
Present invention involves synthesis of alkyds through enzymatic transesterification/ hydrolysis of Vegetable Oils with polyols/ carbohydrates like sorbitol, sucrose as one of the polyol in combination with conventional Polyols.
Presently processes involving Fatty acid, half ester and homogeneity are used for sorbitol-based Alkyd synthesis. However, in alkyd synthesis starting from Vegetable Oil, there is a limitation to use sorbitol as polyol for monoglyceride preparation through transesterification. This limitation could be overcome employing enzymatic transesterification of sorbitol with vegetable oil, as the first step towards alkyd synthesis.
The key added advantages of the present invention are:
1. Processing of transesterification at 40-80°C where conventional transesterification reaction required 240-260°C.
2. 100% sorbitol based (as the lone polyol and without any other co-polyol) alkyd can be made which is difficult through conventional transesterification process.
3. 100% green synthesis of alkyd is possible by using Methyl amyl ketone as a solvent in place of conventional mixed xylene and no esterification catalyst has been used.
According to an aspect of the present invention there is provided a process comprising the steps of
(i) Vegetable Oil and sorbitol were reacted in presence of enzyme wherein reaction mass was heated to 70±2°C and maintained for 8-10 hrs at 70°C and 14-16 hrs at ambient temp of 22-30°C during a 24 hrs cycle and reaction continued for 72 hrs. This provided fatty acid (25-30%) through hydrolysis and monoglyceride/ diglyceride through transesterification;
(ii) Considering high cost of lipase enzyme, the above could be performed at relatively low dosage of Novozym 435 @ 1.5-3%
(iii) alkyd could be synthesized at low monoglyceride content of about 11-32% vis-à-vis 40-65% of conventional/ enzymatic alkyds based on alcoholysis, wherein such alkyd synthesis at low monoglyceride content could be made possible due to the presence of fatty acid obtained from hydrolysis of oil coupled with low monoglyceride content thereby providing compatibility / reactive sites for further reaction with polybasic acid to arrive at desired alkyd resin.
Importantly, in the absence of step (i) of hydrolysis of Oil, the direct alcoholysis reaction with sorbitol resulted in separation/ crystallization of sorbitol and incomplete reaction at such levels as employed in the present invention.
(iv) This enzymatic synthesis of monoglyceride / fatty acid was carried out in presence of water and tert-butanol as solvent;
(v) The process was also carried out wherein immobilized Lipase enzyme was self-contained in a mesh like enclosure built with stirrer to enable reuse of Enzyme multiple times avoiding filtration / loss of expensive enzyme;
(vi) The use of bio based Sorbitol as polyol could be made possible having high Secondary hydroxyl content of about 66% having reduced reactivity over primary hydroxyls.

RM Sources: Raw materials used in the present invention were sourced from companies as a packaged product as detailed below:
Sorbitol 70% (Gulshan Polyols Ltds , Delhi ) ; Glycerine (Jayant Agro Organics Ltd , Mumbai); Phthalic anhydride (Thirumalai Chemicals, Mumbai ) ; Benzoic acid (Ganesh Benzoplast Ltd , Mumbai) ; Refined Palmolein Oil ( Pragji GopalJi , Mumbai ) ; Alkali Refine Soyabean Oil (Cargill India Pvt Ltd ,Gurgaon Haryana); Raw Linseed Oil (Poonam Oil Industries, Indore); Dibutyl Tin Oxide (Elf Atochem Catalyst India Ltd , Mumbai); Hypo phosphorous acid (Anan Drug & Chem Ltd , Bhavnagar Gujarat) , Tertiary Butanol (SD Fine Chem , Mumbai ) , Methyl amyl Ketone ( Eastman Chemicals Ltd ) , Mixed Xylene ( Reliance Industries Ltd , Mumbai ), Mineral Turpentine Oil (Hindustan Petroleum Corporation Ltd, Mumbai)
Enzymes like Novozym 435 (Lipase) , Lipozyme RM IM (Lipase) , Lipozyme TL IM (lipase), Novozym 51003 ( Laccase) , Novozym BAN 480 LS (Alpha Amylase) were procured from Novozymes South Asia Pvt. Ltd. Bangalore.
Iodine value of the oils in the range of 5-200 gm I2 / 100 gm are as per the packaging specifications.

EXAMPLES:
1. Synthesis of Air drying alkyds using Drying/Semi drying oils
Step A : Synthesis of Enzymatically Trans-esterified and hydrolyzed Oil (ETHO)
Ingredients in parts by weight (PBW) ETHO1
(PBW) ETHO2
(PBW) ETHO3
(PBW) ETHO4
(PBW) ETHO5
(PBW) ETHO6
(PBW) ETHO7
(PBW) ETHO8
(PBW)
Alkali Refined soyabean Oil 58.33 80.77 80.77 80.77 80.77 80.77 80.77 ----
Raw Linseed Oil ---- ---- ---- ---- ---- ---- ---- 80.77
Sorbitol (70%) in water 12.5 17.31 17.31 17.31 17.31 17.31 17.31 17.31
Novozym 435 (Lipase) 1.39 1.92 ---- ---- ---- ---- ---- ----
Novozym 435 (Lipase) (Reused) ---- ---- ---- ---- ---- 1.92 ---- ----
Lipozyme RM IM
( Lipase) ---- ---- ---- ---- ---- ---- 1.92 1.92
Lipozyme TL IM (Lipase) ---- ---- 1.92 ---- ---- ---- ---- ----
Novozym 51003 (Laccase) ---- ---- ---- 1.92 ---- ---- ---- ----
Novozym BAN 480 LS
(Alpha Amylase) ---- ---- ---- ---- 1.92 ---- ---- ----
Tert- Butanol 27.78 ---- ---- ---- ---- ---- ---- ----
Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
Analysis
ETHO Tolerance
(Methanol : Ethanol : : 10:3 by volume) 1:3.5 1:2.6 Nil 1:0.5 Nil 1:1.5 1:3 1:2
Acid Value (mg KOH/gm) 61.52 63.875 0.0 31.62 0.0 71.78 86.51 80.41
GPC Analysis
% Monoglyceride 21.40 11.85 Not detected Not detected Not detected 31.09 27.34 30.38

% Diglyceride 22.45 27.87 Not detected Not detected Not detected 24.08 25.30 24.37
% Triglyceride 8.28 27.82 As per Oil content As per Oil content As per Oil content 8.28 8.03 8.13
Fatty Acids 47.88 32.46 Not detected Not detected Not detected 36.55 39.33 37.12

Process for the Synthesis of ETHO1 to ETHO8:
Alkali refined soyabean Oil / Linseed Oil, Sorbitol and enzyme are charged into a 4 necked flask fitted with condenser, stirrer and thermometer. Reaction mass is heated to 70±2°C and maintained for 8-10 hrs at 70°C and 14-16 hrs at ambient temp of 22-30°C during a 24 hrs cycle. Reaction is continued for 72 hrs and samples are withdrawn from 24 hrs onwards at an interval of 6 hrs. This is continued till ETHO sample showed minimum 1: 2 tolerance with solvent mix of Methanol: Ethanol:: 10:3 by volume and acid value of at least 60 (mg KOH /gm). The reaction mass is cooled to ambient temperature, filtered and packed for step B of alkyd synthesis. Further to the abovesaid, ETHO tolerance is an indication of sufficient transesterification of Oil and polyol resulting in mixture of mono/di/ triglycerides and fatty acid. In the absence of such tolerance, phthalic anhydride is not compatible with ETHO resulting in poor reactivity and phase separation in step 2 of alkyd synthesis.
Also the glyceride and fatty acid distribution for ETHO1, ETHO2, ETHO7, ETHO8 depend from the reaction extent such as depends on the reactants, type/concentration of enzyme, reaction temperature and reaction time employed. ETHO 1 and ETHO 2 based on Lipase enzyme are using same ingredient having solvent and aqueous medium respectively. The one in solvent medium has given better transesterification but aqueous medium is the preferred choice for being environmentally safe, non-hazardous and low cost. ETHO 7 is having same composition in aqueous medium as ETHO 2 but different lipase enzyme (Lipozyme RM) providing higher monoglyceride content. ETHO 8 is having similar composition / enzyme as used in as ETHO 7 but with Linseed Oil to interestingly provide for similar composition of mono/di/ triglycerides and fatty acid.
It was found that when the extent of reaction/time and temperature was varied against what is described above for ETHO3-ETHO6, could not facilitate transesterification reaction of Oils with sorbitol as well as hydrolysis of Oils and therefore not suitable for enzymatic synthesis of alkyds, which is reflecting in the low tolerance levels of < 1: 1.5 using solvent mix of Methanol: Ethanol:: 10:3 by volume for ETHO3-ETHO6.
Step B: Synthesis of Alkyds based on ETHO prepared in step A:
Ingredients EA1 (PBW) EA2 (PBW) EA3 (PBW) EA4 (PBW)
ETHO1 64.27 ---- ---- ----
ETHO2 ---- 68.3 ---- ----
ETHO7 ---- ---- 62.9 ----
ETHO8 ---- ---- ---- 62.9
Sorbitol (70%) in water 13.37 ---- ---- ----
Glycerine ---- 5.22 7.52 7.36
Phthalic Anhydride 19.48 23.31 26.31 25.74
Mixed Xylene 2.86 3.15 ---- 3.98
Methyl Amyl Ketone ---- ---- 3.27 ----
Dibutyl Tin Oxide 0.02 0.02 --- ----
Total 100.00 100.00 100.00 100.00
Dilution with Mineral Turpentine Oil (MTO) No dilution Diluted in MTO to required solids Diluted in MTO to required solids Diluted in MTO to required solids
Resin Analysis
Acid Value
(mg KOH /gm) 23.40 17.89 15.78 8.50
Viscosity at 25°C on Gardner V ? W I ? J V ?W Z – Z1
Colour on Gardner 15-16 15-16 14-15 16-17
% NVM @120°C/1hr 95.91% 68.41% 70.15% 63.67
Properties of Clear Coating composition having 0.05% Cobalt Octoate , 0.5% Zirconium Octoate and 0.2% Calcium Octoate as metal content on resin solids and diluted with MTO to application viscosity
Surface dry 4 hrs 2.5 hrs 2 hrs 1.5 hr
Tack free 16 hrs 6.5 hrs 8.5 hrs 4.5 hrs
Hard dry 48 hrs 17 hrs 24 hrs 24 hrs
Dry Fil Thickness- micron 34-39 25-30 24-25 28-30
Gloss at 20° 88 90 92 87
Flow and levelling good Good excellent good
Mechanical Properties
Flexibility on 1/8? mandrel passes Passes Passes Passes
Scratch Hardness 700g 900g 600g 600g
Pencil Hardness 2B Passes 2B Passes 2B Passes 2B Passes
Impact Resistance
Front Passes Passes Passes Passes
Reverse Passes Passes Passes Passes

Process for the synthesis of Alkyds based on ETHO prepared in step A:
Enzymatically trans esterified & hydrolyzed Oil (ETHO) is taken into a 4 necked round bottom flask fitted with condenser, stirrer and thermometer. Rest of the Raw materials like glycerine, sorbitol, Phthalic anhydride, dibutyl tin oxide and xylene /methyl amyl ketone as reflux solvent are charged into the reaction vessel. Initially mixture is heated to 170oC to take out water of sorbitol. Then reaction temperature is slowly raised to 200-210oC until clear solution is obtained. Reaction temperature is further increased to 230-240°C and maintained for 6-12 hrs. Batch is monitored for in-process checks by withdrawing sample at an interval of 1-2 hrs for acid value and Gardner viscosity. Reaction is terminated when desired viscosity and acid value is achieved. Alkyd resin thus obtained is diluted with mineral turpentine oil, cooled to < 120°C, filtered and packed. Alkyds as prepared above tested in clear coating compositions using metallic driers and MTO as solvent.
Experimental Summary for Air drying alkyds:
• Soyabean / linseed oil were used for trans-esterification and hydrolysis with 70% aqueous solution of sorbitol as polyol alongwith variety of immobilized lipase enzymes like Novozym 435, Lipozyme RM IM and Lipozyme TL IM. Trans-esterification and hydrolysis study was also carried out using Laccase (Novozym 51003) and Alpha Amylase like Novozym BAN 480 LS. In experiment ETHO6, Novozyme 435 used earlier was recycled to check its efficacy.

• In ETHO1, tert butanol was used as solvent. Rest of the experiments were carried out in aqueous medium with water coming from sorbitol (70%) solution.

• ETHO samples obtained from the experiments were analyzed for tolerance to Methanol: Ethanol mixture, acid value and compositional analysis through gel permeation chromatography.

• Enzymes which did not provide desired ETHO tolerance with Methanol: Ethanol mixture and acid value failed to provide ETHO having desired reactivity with phthalic anhydride for conversion into alkyds.

• Alkyd EA3 was synthesized without use of esterification catalyst. In this experiment user friendly methyl amyl ketone used as reflux solvent.

• The enzymatically trans esterified and hydrolyzed oil based alkyds enabled 100% use of bio based sugar alcohols i.e. sorbitol as sole polyol in step A and Sorbitol / glycerol in Step B of alkyd synthesis. Alkyds based on enzymatic process showed comparable clear coating properties to that of conventional alkyds.

2 : Synthesis of Forced drying alkyd using non-drying oil
Step A : Synthesis of Enzymatically Trans-esterified and hydrolyzed Oil (ETHO)
Ingredients ETHO 9 (PBW)
Refined Palmolein Oil 80.77
Sorbitol (70%) in water 17.31
Lipozyme RM IM ( Lipase ) 1.92
Total 100.00
Analysis ----
ETHO Tolerance
(Methanol : Ethanol Mixture 10:3 by volume) 1:1.75
Acid Value (mg KOH/gm) 74.18
GPC analysis
% Monoglyceride 7.50
% Diglyceride 25.87
% Triglyceride 32.09
Fatty Acids 34.53

Synthesis Process for ETHO 9:
Refined palmolein oil is heated to 35-45oC to get clear liquid. Refined Palmolein Oil, Sorbitol and enzyme are charged into a 4 necked flask fitted with condenser, stirrer and thermometer. Reaction mass is heated to 70±2°C and maintained for 8-10 hrs at 70°C and 14-16 hrs at ambient temp of 22-30°C during a 24 hrs cycle. Reaction is continued for 72 hrs and samples are withdrawn from 24 hrs onwards at an interval of 6 hrs. Reaction is continued till, ETHO sample shows tolerance of minimum 1 : 1.5 with solvent mix of Methanol : Ethanol : : 10:3( by volume) and acid value (mg KOH /gm ) of min 60 . The reaction mass is cooled to ambient temperature, filtered and packed for step B of alkyd synthesis.
Step B: Synthesis of Alkyds on enzymatically trans-esterified and hydrolyzed oil:
Ingredients EA5 (PBW)
ETHO 9 27.88
Sorbitol (70%) 35.15
Phthalic Anhydride 23.16
Benzoic Acid 8.79
Hypo Phosphorous acid (Anti oxidant ) 0.2
Methyl Amyl Ketone 4.82
Total 100.00
Resin was diluted with mixed xylene to required solids
Resin Analysis
Acid Value (mg KOH /gm) 18.76
Viscosity at 25°C on Gardner Z1-Z2
Colour on Gardner 18+
% NVM @120°C /1 hr 59.43%
Forced Drying Film properties with Melamine formaldehyde resin as crosslinker
Alkyd : Mealmine formaldehyde Resin : : 90:10 on solids
Baking Schedule (150oC for 17 mins)
Mechanical Properties
Flexibility on 1 inch Conical Mandrel Passes
Scratch Hardness 1800 g
Impact Resistance
Front Passes
Reverse Fails
DFT in microns 25-30
Gloss at 20° 92

Process for synthesis of Alkyd based on ETHO 9 prepared in step 2A:
Enzymatically Trans esterified & hydrolyzed Oil mixture is charged into a 4 necked round bottom flask. Rest of the ingredients i.e sorbitol, Phthalic anhydride, antioxidant and reflux solvent are charged into the reaction vessel. Initially mixture is heated to 170oC to remove water from sorbitol. Then reaction temperature is raised slowly to 200-210oC until clear solution is obtained. Reaction temperature is further raised to 235oc and maintained for 8-10 hrs. Batch is monitored for in-process checks by taking sample at an interval of every 45-60 mins for acid value and viscosity. Reaction is terminated when acid value of <20 (mg KOH /gm) and dilution viscosity @ 60% solids in xylene Z1-Z2 is achieved. Resin is cooled and diluted in mixed xylene at < 170°C, filtered and packed. Alkyd thus prepared is used for preparing clear coating solution with melamine formaldehyde resin as crosslinker.
Experimental summary for forced drying alkyd based on non-dying oils:
• Refined Palmolein oil and Sorbitol (70%) is used with Lipozyme RM IM as an enzyme for transesterification & hydrolysis in an aqueous medium.

• Transesterification reaction progress is monitored through minimum 1: 1.5 tolerance of ETHO sample with solvent mix of Methanol : Ethanol : : 10:3 ( by volume) and acid value (mg KOH /gm ) of min 60 .

• Clear Non-drying alkyd resin solution is prepared in xylene at required solids and viscosity.

• This resin sample is tested with amino resin as melamine formaldehyde BM60. The baking cycle is kept as 150oC for 17 mins as that of the control sample.

• The enzymatic transesterification and hydrolysis process enabled synthesis of short oil alkyd based on non-drying palm oil with bio based sugar alcohol i.e. sorbitol as sole polyol. Resultant alkyd provided comparable film properties to the convention alkyd obtained from non-enzymatic process.