A Renewable, Green, and Scalable Polyacrylic Polyol (PAMO) Derived from Olive Oil for Transparent Polyurethane Coatings

A Renewable, Green, and Scalable Polyacrylic Polyol (PAMO) Derived from Olive Oil for Transparent Polyurethane Coatings | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article A Renewable, Green, and Scalable Polyacrylic Polyol (PAMO) Derived from Olive Oil for Transparent Polyurethane Coatings Ehsan Salarvand, Ismail Omrani, Mohammad reza nabid, Milad Salehi This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4620993/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract To prepare a transparent polyurethane coating, a renewable, green, and scalable polyacrylic polyol (PAMO) was synthesized from olive oil (OO) and applied as a polyol. To prepare PAMO, the olive oil was first methanolized using methanol, and methyl oleate (MO) was obtained, followed by its getting epoxidized by formic acid and hydrogen peroxide. Epoxidized methyl oleate (EMO) was ring-opened using acrylic acid (AA) with excellent yield. Further, to prepare PAMO, radical polymerization method was utilized. FT-IR, 1 HNMR, and gel permeation chromatography (GPC) verified the chemical structures of the synthesized monomer and polymer. Different thermoset aliphatic transparent polyurethane coatings were obtained by reacting the synthesized polyol with hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), Desmodur N3390, and Desmodur Z4470. The best results were obtained using Desmodur Z4470 as the curing agent. Polyurethane obtained from PAMO and Desmodur Z4470 was acquired in three NCO/OH ratios of 0.9, 1, and 1.2, with the 1.2 NCO/OH ratio as the best-obtained result. The new polyol architecture has emerged as a new polyacrylic polyol and transparent polyurethane coatings class. acrylic polyol transparent polyurethane coating renewable polyol Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 1. Introduction Polyurethanes (PU) are one of the most widely used polymeric materials that play an important role in human life. Their applications range from medical uses such as orthopedic plaster casts[ 1 ] antimicrobial coatings[ 2 ] and drug delivery[ 3 ] to industrial applications such as adhesives[ 4 , 5 ], foams[ 6 , 7 ], sealants[ 8 , 9 ], elastomers[ 10 , 11 ], and coatings. The reaction between a polyisocyanate and a polyol produces polyurethanes[ 12 ]. Various polyols are used to generate polyurethane products. The three most common polyols in polyurethane systems include polyester polyols, polyether polyols, and polyacrylic polyols. Polyacrylic polyols are more common in polyurethane coatings[ 13 , 14 ]. Polyurethane films and coatings made with this type of polyols show excellent gloss characteristics, good physical and mechanical properties, good chemical stability, low-temperature flexibility, and good outdoor performance[ 15 , 16 ]. However, concerns have been raised about the use of petrochemical derivatives due to the exhaustion of fossil feedstock[ 17 – 19 ], undesirable characteristics such as a low degradability rate[ 20 ], global warming[ 21 ], and their volatile organic compounds (VOC)[ 22 , 23 ]. Renewable raw materials have been replaced with oil derivatives to address this pitfall. Among the renewable materials, vegetable oils have been selected to convert cured raw materials into valuable industrial materials[ 24 ] due to their advantages, such as being economical[ 25 , 26 ], energy recovery[ 27 ], and their abundance[ 28 , 29 ].Vegetable oils are triglycerides of fatty acids, which, according to their type, have different chain lengths of 16–20 and 0–3 carbon-carbon double bonds per chain. Although oils have been directly used in some industries[ 30 , 31 ], most crude oils typically are required to be modified before chemical consumption. Despite the presence of various active sites (e.g, allylic carbons, ester group, carbon alpha to the ester group, bisallylic position, etc.)[ 32 ], and different methods (hydroformylation and hydrogenation, ozonolysis, esterifications, etc)[ 33 , 34 ], industrial functionalization oils are usually created by epoxidation of double bonds[ 35 – 37 ], followed by ring-opening with compounds containing active hydrogen[ 35 , 38 – 42 ]. Triglyceride and fatty acids are widely used to manufacture polyether polyol and polyester polyol for polyurethanes[ 43 ]. As examples, Narute et al, prepared a polyol by epoxidation of linseed oil and then oxirane ring-opening with water and reaction with polyisocyanate with a different NCO/OH ratio[ 44 ]. They found that increasing the amount of NCO improves mechanical properties such as storage modulus, adhesive, and strength. Gaikwad et al., synthetized polyols by oxirane ring-opening of epoxidized cottonseed and Karanja oils with polyethylene glycol (The molecular weight of PEG varied from 200 to 600 g/mol) and varied isocyanates (MDI, TDI, IPDI), leading to a polyurethane coating with good characteristics[ 45 ]. Applying simultaneously oxirane ring-opening and esterification of five oils (Canola Oil, Sunflower Oil, Flax Oil, Camelina Oil, and Canola Oil) with 1,3propanediol, Xiaohua Kong et al., synthesized a series of polyols with high functionality and low viscosity. It is noteworthy that all of the polyurethanes prepared by the reaction of this polyol and PMDI have good thermal-mechanical characteristic[ 46 ]. Also, using cationic oxirane ring-opening of epoxidized methyl oleate (EMO), Lligadas et al., synthesized an oligomeric polyether polyol[ 47 ]. Junming et al., synthesized a polyester polyol by dihydroxylation EMO and then with esterification by glycerol[ 48 ]. Despite extensive studies on preparing polyester polyol and polyether polyol from vegetable oils, the synthesis of polyacrylic polyols from these sources is underresearched. The increasing attention to acrylic-based transparent polyurethane coatings, the disadvantages of petroleum derivatives, and the advantages of vegetable oils were the major stimuli that drove us toward the design and synthesis of a hydroxyl-bearing acrylic monomer containing an internal plasticizer. The bio-based monomer was synthesized by epoxidation of MO, followed by oxirane ring-opening by AA. The polyacrylic polyol made by free radical polymerization of AMO has an OH number of approximately 100, which is suitable for coating applications. The synthesized polyol has acrylic segments and dangling chain segments that offer unique properties. The characteristics of the designed polyol are within the range of acrylic polyols commonly used in the polyurethane coating industry. 2. Experimental 2.1 Materials Unrefined olive oil was purchased from the local market. methanol (CH3OH), sodium hydroxide (NaOH), hydrogen peroxide (H2O2, 35%, w/v), sulfuric acid (H2SO4, 98%), formic acid (HCOOH, 99% aqueous), acrylic acid (AA) with purity of 99.8%, N,N-dimethycyclohexylamine (DMCHA) with purity of 98%, dry methyl ethyl ketone (MEK), azobisosobutyronitrile (AIBN), Magnesium sulfate anhydrous (MgSO4), Dibutyltin dilaurate (DBTDL), HDI, and IPDI were purchased from Merck Co. Desmudur Z4470, Desmudur N3390, purchased from Bayer co. and leveling agent BYK 3550 was obtained from BYK Co. 2.2 Synthesis of methyl oleate (MO) The methyl oleate was prepared from the transesterification of olive oil (acid value = 1.1mgKOH/g). 100g olive oil and 110g methanol and 0.3g NaOH were added to a 0.5litr two-necked flask equipped with a condenser and thermometer. The mixture was stirred for 5h at reflux temperature. It was then allowed 10 minutes to settle the formed glycerol. Next, MO was placed in a decanter and washed out three times with saturated sodium chloride solution, followed by drying over manganese sulfate. Acid value of MO was measured by about 0.9 mgKOH/g. 2.3 Epoxidation of methyl oleate (EMO) 50g MO, 8g HCOOH and 0.28g sulfuric acid were added to a reaction vessel equipped with a thermometer, a condenser, and a dropping funnel. The mixture was vigorously stirred for 15 minutes at room temperature. Then, 48g H2O2 was added to the mixture dropwise for 1 h. At the time of adding H2O2, the temperature of the mixture was maintained between 30°C and 40°C. The reaction continued for 7 hours. Finally, the mixture was washed with saturated sodium chloride and dried with manganese sulfate. Acid value of EMO was measured by 1 mgKOH/g. 2.4 Acrylation of epoxidized methyl oleate (AMO) Acrylated methyl oleate (AMO) was obtained from the oxirane ring-opening of EMO by Acrylic acid (AA). EMO and AA with a 1:4 molar ratio were added to a two-necked round bottom flask, and DMCHA 2% as the same weight as AA was added. The mixture was stirred and heated to 65°C for 30 hours. The organic phase was extracted using dichloromethane and washed with a saturated sodium chloride solution until the PH was naturalized. Acid value of EMO was measured by 1.3 mgKOH/g. 2.5 Preparation of bio-based acrylic polyol (PAMO) The biobased acrylic polyol was obtained by solution polymerization of AMO. 50g AMO, 0.01g AIBN, and 50% of toluene weight were added to a four-necked round bottom flask equipped with a thermometer, condenser, nitrogen sparger inlet, and rubber septum. The system was completely sealed. First, 15 minutes of nitrogen was purged, and then the temperature reached 40°C to dissolve AIBN, followed by the temperature reaching 80°C for 10 h. The reaction product was transferred to a Petri dish and stored overnight at 50°C in a vacuum oven. A Polyol with high viscosity was obtained in a transparent and colorless form with 90 mg/gKOH hydroxyl number. 2.6 Preparation of Polyurethane coatings A series of polyurethane coatings was acquired by PAMO reaction with Desmodur Z4470, N3390, and IPDI at various NCO/OH ratios. The isocyanate content of the three isocyanates was measured, which can be seen in Table 1 . A certain amount of polyol and Desmudure Z4470 based on the NCO/OH ratio, 50% by weight of the mixture MEK, a trace amount of DBTDL, and 0.05% by weight BYK 3550 were poured into a two-necked round bottom flask equipped with a condenser, and a mechanical stirrer. The mixture reached 40–50°C for 30 minutes. Then, this mass was transferred into a preheated mild steel at a thickness of 150 µm and put in vacuum oven at 40°C for 24h. The oven temperature was then increased to 80°C for 2 days. All samples with different equivalent ratios were prepared using the method described above. Table 1 Isocyanate content of (IPDI, Desmodur N3390 and Desmodur Z4470) Isocyanate HDI IPDI Desmodur N3390 Desmodur Z4470 NCO content 49.9 ± 0.3 37.5 ± 0.3 19.6 ± 0.3 11.9 ± 0.4 2.7 Characterization The characterization of 1HNMR spectra was recorded on a Bruker Avance operating at a frequency of 300 MHz using tetramethylsilane (TMS) as an internal standard and CDCl3 as solvents. Infrared spectra from 400 to 4000 cm-1 were recorded on a Shimadzu 470 FT-IR instrument, using potassium bromide pellets. Gel permeation chromatography (GPC) was performed on Agilent Tech., Model 1260 infinity equipped with a differential refractometer and mixed column. Tetrahydrofuran (1.0 mL/min) was used as the eluent at 30 ± 1°C. Differential scanning calorimetry (DSC) experiments were performed using a TA DSC Q200 calorimeter under a nitrogen atmosphere. The sample was heated to 120°C at a heating rate of 10°C min-1. Gloss was measured at an angle of 45° on a digital glossmeter RSPT-20 by ASTM D2457–13. The hardness of the coatings was measured by Shore A Zwick Roell by ASTM D 2240. The scratch resistance of the samples was measured using the automatic scratch tester Rajdhani. Acid value of OO, MO, EMO, AMO was measured by ASTM D7253 method. The precision thickness of the coatings was measured by CMI155 HITACHI. The hydroxyl number of Polyol (PAMO) was determined by ASTM D4274 test method D. The isocyanate content of HDI, IPDI, Desmodur N3390, and Desmodur Z4470 was measured by ASTM D2572-97. The adhesion test was performed using a crosscut adhesion tester (model no. 107, elcometer, UK) and ASTM D-3395a. 3. Results and Discussion 3.1 Synthesis of monomer and polymer As presented in Fig. 1 , the monomer AMO was synthesized from olive oil by methanolysis, epoxidation, and ring-opening reaction. If we directly epoxidize the olive oil and then polymerize it, the polyol would become a gel before forming because the number of double bonds on the monomer would be increased to 3, that is, 3 polymerization sites in one monomer. This is also the reason why we did not use other oils. As shown in Fig. 2 , the bio-based acrylic polyol (PAMO) was prepared by solution radical polymerization initiated using AIBN. The transparent thermoset polyurethane coating was obtained by the reaction of bio-based acrylic polyol and isocyanates (Fig. 3 ). FTIR, 1HNMR, GPC, viscosity, and hydroxyl number followed the conversion of functional groups. As shown in Fig. 4 , the FTIR spectrum of olive oil, MO, EMO, AMO, and PAMO was compared. The peak around 1720 cm-1 is related to the carbonyl group, and the peak at 3008 cm-1 is related to the C-H of the unsaturated band of the oil chains. Comparing the fingerprint region of the MO spectrum with the OO made it possible to find the synthesized MO successfully. In the FTIR spectrum of EMO, the peak of region 3008 cm-1 belonging to the H-C bond attached to the C = C disappeared, and a very low-intensity peak at 830 cm − 1 belonging to the (C-O) group was raised in the FTIR of EMO. This is a reason for the complete conversion of the double band to the epoxy group. The reaction of epoxy groups and acrylic acid was confirmed by the appearance of peaks at 810 cm-1, 984 cm-1, 1406 cm-1, and 1635 cm-1 related to the C-H bonds of acrylic groups and the broad peak in 3500–3700 cm-1 belonged to the H-O bonds. Free radical polymerization of synthesized bio-based monomer initiated by benzoyl peroxide was monitored using FTIR. The peaks related to the acrylic group disappeared. As shown in Fig. 5 , the chemical structure of the products was confirmed using 1HNMR. The 1HNMR spectrum of olive oil is illustrated in Fig. 5 . The peak area of 0.9 ppm corresponds to the methyl groups at the end of the carbon chain oil, the peak area of 2.1 ppm corresponds to CH2 attached to the carbonyl group, the peak area of 4.6 to 4.8 ppm is related to CH and CH2 on the glycerol and the area 5.8 ppm is related to the double bond hydrogen. With methanolysis reaction, the triglyceride is converted to methyl ester which resulted in the elimination of CH2 and CH peaks attached to ester groups, approving the complete conversion of triglyceride into methyl ester. 1HNMR confirmed the epoxidation of the C = C bond. In the EMO 1 HNMR spectrum, the disappearance of the peak in region 5.8 ppm and the appearance of the peak in region 2.8 ppm corresponding to hydrogen attached to the epoxy ring group indicate the complete conversion of the double bond to the epoxy group. With the ring-opening of the epoxy group by acrylic acid, the peak at 2.9 ppm, which belonged to hydrogen attached to the epoxy group, became invisible. The peaks in the region of 5.75 to 6.5 ppm are related to the C–H bonds of the unsaturated acrylic group in AMO, and 4.8 ppm are related to C-H bonds attached to the ester group formed from the reaction of acrylic acid and epoxy groups. Finally, the disappearance of peaks at 5.8 to 6.5 ppm confirms that the polymerization of the double bonds of AMO was successfully performed. The free radical polymerization of the bio-based monomer to bio-based acrylic polyol was studied using GPC. The GPC chromatogram of PAMO is shown in Fig. 6 . Notably, two peaks of different molecular weights are observed in the PAMO chromatogram. The first pick with a molecular weight of 12712 gr/mol is related to PAMO, and the second pick with a molecular weight of approximately 300 gr/mol and narrow distribution molecular weight is related to the methyl oleate chain, which has no C = C functionality and remains unchanged in the mixture. It is advantageous for a bio-based acrylic coating system that acts as a plasticizer in a polyurethane network. The general specifications of the GPC chromatogram of bio-based PAMO are shown in Table 2 . Appling theoretical calculations, we can see that the average of monomers in each chain is 33: Table 2 GPC data of PAMO Mn 12712 g/mol Mw 30678/mol Mz 87637/mol PDI 2.413 where DP denotes the degree of polymerization, m signifies the molecular weight of the monomer, and Mn symbolizes the average molecular weight of the polymer chain. The polydispersity index (PDI) of polymerization was approximately 2.4. This is acceptable because of the radical polymerization method. There are many chain transfer reactions in solution radical polymerization, such as chain transfer to solvent, chain transfer to monomer, chain transfer to the polymer chain, etc., that make PDI increase. 3.2 Preparation of the transparent polyurethane coating Four types of polyurethane were prepared by PAMO reaction with HDI, IPDI, Desmodur N3390, and Desmodur Z4470 in different NCO/OH ratios as summarized in Table 3 . Based on the study, the selected isocyanates due to the unique properties of aliphatic polyurethane coating are most suitable for synthesized bio-based acrylic polyol. The chemical structure of the isocyanates is depicted in Fig. 7 . The IPDI and HDI are difunctional isocyanates and Desmodur N3390 and Desmodur Z4470 are trifunctional isocyanates. The prepared polyurethanes coating with Desmodur N3390 and Desmodur Z4470 have more cross-linking than HDI and IPDI. The resistance of a polymer to the penetration of a hard object is called the hardness of a polymer. It is notable that if the polyol parameters remain constant, the hardness and scratch resistance of the coating is changed by the isocyanate as follows: Table 3 Coating properties of prepared polyurethane with different isocyanate sample Isocyanate Hardness Shore A Gloss Scratch resistance (gr) Crosscut adhesion PU-1 HDI 59 86 200–250 29 PU-2 IPDI 60 88 200–250 30 PU-3 Desmodur N3390 67 90 250–300 28 PU-4 Desmodur Z4470 76 93 300–350 20 Desmodur Z4470 > Desmodur N3390 > IPDI > HDI This trend can be attributed to the higher functionality of Desmodur Z4470 and Desmodur N3390, which cause higher crosslinking of the coating and the existence of aliphatic and isocyanurate rings in Desmodur Z4470. The presence of isocyanurate and aliphatic rings increases the hardness and scratch resistance of the polyurethane coating. The above trend can be interpreted according to the structure of these isocyanates, as shown in Fig. 3 . The gloss of the coatings does not change much with the change in the isocyanates. All bio-based polyurethane coatings exhibit excellent gloss. As one of the characteristics of polyacrylic polyols is the high gloss of their coatings, it can be concluded that the high gloss of these coatings is related to the bio-based synthesized polyol. The dangling chains on the polymer backbone seem to be the origin of high glossiness. The mobile dangle chain prevents the close packing of the urethane groups. One of the notable features of the prepared polyurethane coatings is transparency as well as gloss Fig. 8 . Gloss is an optical property of coatings. As the light beams reach the surface of the coating, some beams pass through the coating. Part of these light beams is reflected and partly diffused. The gloss of a coating depends on how much light the reflection reflects and how much light is diffused. On the other hand, the transparency of the coating depends on the amount of light that passes through the polymer chain of coatings. In the prepared polyurethane coatings, dangling chains of oil cause the polymer chains to move away from each other so the light beam will pass through them. The prepared polyurethanes' adhesion to metal surfaces was studied. All samples indicated excellent adhesion to the surface due to the presence of the ester group of the polyol and urethane groups. It was observed that the metal adhesion properties of sample 3 were higher than those of samples 1 and 2. It seemed the higher adhesion was raised from the isocyanurate ring on Desmodur z4470. It was found that the coating properties of sample 3 proved better than those of samples 1 and 2. Three polyurethane coatings with different NCO/OH (0.9, 1, and 1.2) ratios were prepared. The coating properties of prepared bio-based polyurethanes were measured; the results are listed in Table 4 . The hardness and scratch resistance increase with increasing amounts of NCO/OH. As NCO/OH increases from 0.9 to 1, the urethane groups increase, resulting in increased hardness and scratch resistance. When the NCO/OH ratio changes from 1 to 1.2, the excess NCO groups react with air humidity and form urea groups, which increase the crosslink density and hardness and scratch resistance (Fig. 9 ). Increasing the crosslink density results in forming a smooth surface, increasing light reflection, and improving the brightness of the coatings. It is also observed that in 1.2 NCO/OH ratio, the adhesion to the metal increases. The urea groups are likely to increase the adhesion of the coating to the metal. The glass transition temperatures (Tg) and the melting point of the prepared polyurethane coating were determined after the second scan, which are shown in Fig. 10 . The DSC spectra were obtained from three polyurethane coatings Pu-3-1, Pu-3-2, and Pu-3-3 made from PAMO and Desmodur Z4470. The resulting bio-based polyurethane network is three-dimensional because the designed biobased polyol is highly functional, and it appears that all the crosslinks are not covalent bands and some of them are hydrogen bands. It means that urethane and urea linkages are enhanced with an increase in NCO/ OH ratio, leading to more cross-linking densities that limit the polymer mobility. As NCO/OH ratios affect the thermal and mechanical behaviors of the polyurethane coating, the Tg values and the thermal properties of the prepared samples are influenced by the NCO/OH ratio as well. As the NCO/OH ratio increases from 0.9 to 1.2 molar ratio, the Tg values increases from 54 to 85°C, respectively. It seems transfer in region 129°C is related to the separation of the urethane-urethane hydrogen bonds and temperature transfer above 199 ° C is related to the heat degradation of polyurethane. Table 4 Coating properties of prepared polyurethane with different NCO/OH sample NCO/OH Hardness Shore A Gloss Scratch resistance (gr) Crosscut adhesion Pu-4-1 0.9 65 90 250–300 22 Pu-4-2 1 73 93 300–350 22 Pu- 4 − 3 1.2 80 96 300–350 17 4. Conclusion In conclusion, we designed and synthesized novel bio-based polyacrylic polyols and explored their coating properties for transparent and glossy polyurethane coating. In the first step, polyacrylic polyol was successfully synthesized by methanolysis of olive oil, epoxidation of the double bond, and oxirane ring-opening by acrylic acid. In the second step, the monomer was polymerized by solvent radical polymerization. The chemical structure of intermediates and polyol was verified by FT-IR, 1HNMR, and GPC. The obtained polyacrylic polyol reacted with four types of isocyanates (HDI, IPDI, Desmodur N3390, and Desmodur Z4470) and polyurethane coatings. Considering that the best results were obtained from Desmodur Z4470, we synthesized three NCO/OH ratios from PAMO and Desmodur Z4470, and evaluated their physical properties. The best results were obtained with the PAMO polyol and the Desmodur Z4470 isocyanate with a ratio of 1.2. The results show that it is possible to actuate olive oil based polyacrylic polyol to produce a unique and useful material. In other words, the prepared bio-based polyurethanes with high gloss are usable as transparent films and are important in the coating industry. Declarations Conflict of Interest The authors declare no conflicts of interest. Author Contribution Author ContributionsEhsan Salarvand fed the data to the software, carried out the analysis, wrote the original draft and the methodology. Ismail Omrani undertook the conceptualization, project administration, and writing - the original draft. Milad Salehi embarked on the review and editing. 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J Am Oil Chem Soc 84:929–935 Kovash CS Jr, Pavlacky E, Selvakumar S et al (2014) Thermoset coatings from epoxidized sucrose soyate and blocked, bio-based dicarboxylic acids. Chemsuschem 7:2289–2294 Monteavaro LL, da Silva EO, Costa APO et al (2005) Polyurethane networks from formiated soy polyols: synthesis and mechanical characterization. J Am Oil Chem Soc 82:365–371 Narute P, Palanisamy A (2016) Study of the performance of polyurethane coatings derived from cottonseed oil polyol. J Coat Technol Res 13:171–179 Gaikwad MS, Gite VV, Mahulikar PP et al (2015) Eco-friendly polyurethane coatings from cottonseed and karanja oil. Prog Org Coat 86:164–172 Kong X, Liu G, Qi H, Curtis JM (2013) Preparation and characterization of high-solid polyurethane coating systems based on vegetable oil derived polyols. Prog Org Coat 76:1151–1160 Lligadas G, Ronda JC, Galia M et al (2006) Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources. J Polym Sci Polym Chem 44:634–645 Junming X, Jianchun J, Jing L (2012) Preparation of polyester polyols from unsaturated fatty acid. J Appl Polym Sci 126:1377–1384 Additional Declarations No competing interests reported. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4620993","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":318180461,"identity":"867fd5a9-86a6-4e2e-b881-df9394bb6ca9","order_by":0,"name":"Ehsan Salarvand","email":"","orcid":"","institution":"Shahid Beheshti University","correspondingAuthor":false,"prefix":"","firstName":"Ehsan","middleName":"","lastName":"Salarvand","suffix":""},{"id":318180463,"identity":"eaff26ad-a93d-413f-9bdc-c504a1c1f921","order_by":1,"name":"Ismail Omrani","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAw0lEQVRIiWNgGAWjYBACNijNw88MJBNATGZitUg2E6sFDgwOEKuSj4H56OaKmjsyxsd5jz14wGAnz8DO+4CAw9jSbp459ozH7DBfukECQ7JhAzO7AQEtPGY3G9gOA7XwmEkkMDADERteHVAt/w7zGDeDtdQTqaWx7TCPATNYy2EitDAD/dLYd5hHAuwXg+OGbYS0yLc3H7vZ8O2wPX//2WMPf1RUy/PzH8OvBSnieICmGyAilxjAQ4riUTAKRsEoGEkAANYrM8IiMABoAAAAAElFTkSuQmCC","orcid":"","institution":"Iran Polymer and Petrochemical Institute","correspondingAuthor":true,"prefix":"","firstName":"Ismail","middleName":"","lastName":"Omrani","suffix":""},{"id":318180464,"identity":"e079d11d-565d-4cd4-bc23-00a2f3f11dcc","order_by":2,"name":"Mohammad reza nabid","email":"","orcid":"","institution":"Shahid Beheshti University","correspondingAuthor":false,"prefix":"","firstName":"Mohammad","middleName":"reza","lastName":"nabid","suffix":""},{"id":318180465,"identity":"7f8ffb77-0008-45f6-82ee-b567b8524e95","order_by":3,"name":"Milad Salehi","email":"","orcid":"","institution":"Shahid Beheshti University","correspondingAuthor":false,"prefix":"","firstName":"Milad","middleName":"","lastName":"Salehi","suffix":""}],"badges":[],"createdAt":"2024-06-22 08:47:30","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4620993/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4620993/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":60307823,"identity":"8a5bae23-6dac-417d-9a1e-1dcd4bbb1e85","added_by":"auto","created_at":"2024-07-15 12:10:39","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":33894,"visible":true,"origin":"","legend":"\u003cp\u003eSynthesis route of AMO from olive oil\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/829a801ddbafe54365a66be2.png"},{"id":60307826,"identity":"a5442671-74e7-43f2-b7e4-c80deb07c845","added_by":"auto","created_at":"2024-07-15 12:10:40","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":137014,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic presentation of radical polymerization of AMO\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/3a4b5741c111d1d1ee47a438.png"},{"id":60308613,"identity":"26b49282-dce5-4cf4-a3d8-1b465596ee0e","added_by":"auto","created_at":"2024-07-15 12:18:40","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":250801,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic reaction of PAMO and three isocyanates for preparation PU coatings\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/f32f8afcef2b16f6a665dda0.png"},{"id":60307824,"identity":"a7d95ca2-4229-410a-9828-02862fa9df72","added_by":"auto","created_at":"2024-07-15 12:10:39","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":159463,"visible":true,"origin":"","legend":"\u003cp\u003eFR-IR of OO, MO, EMO, AMO, PAMO\u003c/p\u003e","description":"","filename":"floatimage5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/8a15a911045647363267bf5a.jpeg"},{"id":60308612,"identity":"7e939917-0cf4-4496-a6eb-f33159c829f2","added_by":"auto","created_at":"2024-07-15 12:18:39","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":33846,"visible":true,"origin":"","legend":"\u003cp\u003e1HNMR of OO, MO, EMO, AMO, PAMO\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/9e1a2d35851ae665e800434c.png"},{"id":60307820,"identity":"4f969acc-0678-4207-afd2-aa048b75c626","added_by":"auto","created_at":"2024-07-15 12:10:38","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":167051,"visible":true,"origin":"","legend":"\u003cp\u003eGPC chromatogram of PAMO\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/2af8e54e138b089a6da62143.png"},{"id":60307821,"identity":"903b3115-9734-426e-97fd-37ec3efa693c","added_by":"auto","created_at":"2024-07-15 12:10:39","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":25818,"visible":true,"origin":"","legend":"\u003cp\u003eChemical structure of isocyanates\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/3f4b46b1217959ff94d18760.png"},{"id":60307827,"identity":"f1e7ccf1-6bc5-492b-9683-6b27f53818c6","added_by":"auto","created_at":"2024-07-15 12:10:40","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":131267,"visible":true,"origin":"","legend":"\u003cp\u003eGloss and transparent polyurethane coatings\u003c/p\u003e","description":"","filename":"floatimage9.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/9b4dd084c7c01801a1ccaa31.png"},{"id":60307822,"identity":"fa6af4bf-d316-4753-a1a5-705ee5e9f2b4","added_by":"auto","created_at":"2024-07-15 12:10:39","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":81552,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of increasing NCO/OH ratio on crosslink density\u003c/p\u003e","description":"","filename":"floatimage10.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/3ef30b11d55f496a76285cf3.png"},{"id":60307819,"identity":"3df7a62b-d851-4b4c-83ce-69efbe76e390","added_by":"auto","created_at":"2024-07-15 12:10:38","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":135510,"visible":true,"origin":"","legend":"\u003cp\u003eDSC thermograms (10°C/min) of Pu coatings with different NCO/OH ratios\u003c/p\u003e","description":"","filename":"floatimage11.png","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/e1c8044d402409ffdf0959a0.png"},{"id":62347861,"identity":"176f67b3-42ef-4890-8cea-0f9003544e31","added_by":"auto","created_at":"2024-08-13 07:38:04","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1628502,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4620993/v1/aa642d97-2017-44bb-894a-5f4bcc3e0d86.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"A Renewable, Green, and Scalable Polyacrylic Polyol (PAMO) Derived from Olive Oil for Transparent Polyurethane Coatings","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003ePolyurethanes (PU) are one of the most widely used polymeric materials that play an important role in human life. Their applications range from medical uses such as orthopedic plaster casts[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e] antimicrobial coatings[\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e] and drug delivery[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e] to industrial applications such as adhesives[\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e], foams[\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e], sealants[\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], elastomers[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e], and coatings. The reaction between a polyisocyanate and a polyol produces polyurethanes[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. Various polyols are used to generate polyurethane products. The three most common polyols in polyurethane systems include polyester polyols, polyether polyols, and polyacrylic polyols. Polyacrylic polyols are more common in polyurethane coatings[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. Polyurethane films and coatings made with this type of polyols show excellent gloss characteristics, good physical and mechanical properties, good chemical stability, low-temperature flexibility, and good outdoor performance[\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. However, concerns have been raised about the use of petrochemical derivatives due to the exhaustion of fossil feedstock[\u003cspan additionalcitationids=\"CR18\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e], undesirable characteristics such as a low degradability rate[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e], global warming[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e], and their volatile organic compounds (VOC)[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. Renewable raw materials have been replaced with oil derivatives to address this pitfall. Among the renewable materials, vegetable oils have been selected to convert cured raw materials into valuable industrial materials[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e] due to their advantages, such as being economical[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e], energy recovery[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e], and their abundance[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].Vegetable oils are triglycerides of fatty acids, which, according to their type, have different chain lengths of 16\u0026ndash;20 and 0\u0026ndash;3 carbon-carbon double bonds per chain.\u003c/p\u003e \u003cp\u003eAlthough oils have been directly used in some industries[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e], most crude oils typically are required to be modified before chemical consumption. Despite the presence of various active sites (e.g, allylic carbons, ester group, carbon alpha to the ester group, bisallylic position, etc.)[\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e], and different methods (hydroformylation and hydrogenation, ozonolysis, esterifications, etc)[\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e], industrial functionalization oils are usually created by epoxidation of double bonds[\u003cspan additionalcitationids=\"CR36\" citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e], followed by ring-opening with compounds containing active hydrogen[\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e, \u003cspan additionalcitationids=\"CR39 CR40 CR41\" citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e]. Triglyceride and fatty acids are widely used to manufacture polyether polyol and polyester polyol for polyurethanes[\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eAs examples, Narute et al, prepared a polyol by epoxidation of linseed oil and then oxirane ring-opening with water and reaction with polyisocyanate with a different NCO/OH ratio[\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. They found that increasing the amount of NCO improves mechanical properties such as storage modulus, adhesive, and strength. Gaikwad et al., synthetized polyols by oxirane ring-opening of epoxidized cottonseed and Karanja oils with polyethylene glycol (The molecular weight of PEG varied from 200 to 600 g/mol) and varied isocyanates (MDI, TDI, IPDI), leading to a polyurethane coating with good characteristics[\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. Applying simultaneously oxirane ring-opening and esterification of five oils (Canola Oil, Sunflower Oil, Flax Oil, Camelina Oil, and Canola Oil) with 1,3propanediol, Xiaohua Kong et al., synthesized a series of polyols with high functionality and low viscosity. It is noteworthy that all of the polyurethanes prepared by the reaction of this polyol and PMDI have good thermal-mechanical characteristic[\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e]. Also, using cationic oxirane ring-opening of epoxidized methyl oleate (EMO), Lligadas et al., synthesized an oligomeric polyether polyol[\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e]. Junming et al., synthesized a polyester polyol by dihydroxylation EMO and then with esterification by glycerol[\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eDespite extensive studies on preparing polyester polyol and polyether polyol from vegetable oils, the synthesis of polyacrylic polyols from these sources is underresearched. The increasing attention to acrylic-based transparent polyurethane coatings, the disadvantages of petroleum derivatives, and the advantages of vegetable oils were the major stimuli that drove us toward the design and synthesis of a hydroxyl-bearing acrylic monomer containing an internal plasticizer. The bio-based monomer was synthesized by epoxidation of MO, followed by oxirane ring-opening by AA. The polyacrylic polyol made by free radical polymerization of AMO has an OH number of approximately 100, which is suitable for coating applications. The synthesized polyol has acrylic segments and dangling chain segments that offer unique properties. The characteristics of the designed polyol are within the range of acrylic polyols commonly used in the polyurethane coating industry.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003eUnrefined olive oil was purchased from the local market. methanol (CH3OH), sodium hydroxide (NaOH), hydrogen peroxide (H2O2, 35%, w/v), sulfuric acid (H2SO4, 98%), formic acid (HCOOH, 99% aqueous), acrylic acid (AA) with purity of 99.8%, N,N-dimethycyclohexylamine (DMCHA) with purity of 98%, dry methyl ethyl ketone (MEK), azobisosobutyronitrile (AIBN), Magnesium sulfate anhydrous (MgSO4), Dibutyltin dilaurate (DBTDL), HDI, and IPDI were purchased from Merck Co. Desmudur Z4470, Desmudur N3390, purchased from Bayer co. and leveling agent BYK 3550 was obtained from BYK Co.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of methyl oleate (MO)\u003c/h2\u003e \u003cp\u003eThe methyl oleate was prepared from the transesterification of olive oil (acid value\u0026thinsp;=\u0026thinsp;1.1mgKOH/g). 100g olive oil and 110g methanol and 0.3g NaOH were added to a 0.5litr two-necked flask equipped with a condenser and thermometer. The mixture was stirred for 5h at reflux temperature. It was then allowed 10 minutes to settle the formed glycerol. Next, MO was placed in a decanter and washed out three times with saturated sodium chloride solution, followed by drying over manganese sulfate. Acid value of MO was measured by about 0.9 mgKOH/g.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Epoxidation of methyl oleate (EMO)\u003c/h2\u003e \u003c/div\u003e\n\u003ch3\u003e50g MO, 8g HCOOH and 0.28g sulfuric acid were added to a reaction vessel equipped with\u003c/h3\u003e\n\u003cp\u003ea thermometer, a condenser, and a dropping funnel. The mixture was vigorously stirred for 15 minutes at room temperature. Then, 48g H2O2 was added to the mixture dropwise for 1 h. At the time of adding H2O2, the temperature of the mixture was maintained between 30\u0026deg;C and 40\u0026deg;C. The reaction continued for 7 hours. Finally, the mixture was washed with saturated sodium chloride and dried with manganese sulfate. Acid value of EMO was measured by 1 mgKOH/g.\u003c/p\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Acrylation of epoxidized methyl oleate (AMO)\u003c/h2\u003e \u003cp\u003eAcrylated methyl oleate (AMO) was obtained from the oxirane ring-opening of EMO by Acrylic acid (AA). EMO and AA with a 1:4 molar ratio were added to a two-necked round bottom flask, and DMCHA 2% as the same weight as AA was added. The mixture was stirred and heated to 65\u0026deg;C for 30 hours. The organic phase was extracted using dichloromethane and washed with a saturated sodium chloride solution until the PH was naturalized. Acid value of EMO was measured by 1.3 mgKOH/g.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Preparation of bio-based acrylic polyol (PAMO)\u003c/h2\u003e \u003cp\u003eThe biobased acrylic polyol was obtained by solution polymerization of AMO. 50g AMO, 0.01g AIBN, and 50% of toluene weight were added to a four-necked round bottom flask equipped with a thermometer, condenser, nitrogen sparger inlet, and rubber septum. The system was completely sealed. First, 15 minutes of nitrogen was purged, and then the temperature reached 40\u0026deg;C to dissolve AIBN, followed by the temperature reaching 80\u0026deg;C for 10 h. The reaction product was transferred to a Petri dish and stored overnight at 50\u0026deg;C in a vacuum oven. A Polyol with high viscosity was obtained in a transparent and colorless form with 90 mg/gKOH hydroxyl number.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e2.6 Preparation of Polyurethane coatings\u003c/h2\u003e \u003cp\u003eA series of polyurethane coatings was acquired by PAMO reaction with Desmodur Z4470, N3390, and IPDI at various NCO/OH ratios. The isocyanate content of the three isocyanates was measured, which can be seen in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. A certain amount of polyol and Desmudure Z4470 based on the NCO/OH ratio, 50% by weight of the mixture MEK, a trace amount of DBTDL, and 0.05% by weight BYK 3550 were poured into a two-necked round bottom flask equipped with a condenser, and a mechanical stirrer. The mixture reached 40\u0026ndash;50\u0026deg;C for 30 minutes. Then, this mass was transferred into a preheated mild steel at a thickness of 150 \u0026micro;m and put in vacuum oven at 40\u0026deg;C for 24h. The oven temperature was then increased to 80\u0026deg;C for 2 days. All samples with different equivalent ratios were prepared using the method described above.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eIsocyanate content of (IPDI, Desmodur N3390 and Desmodur Z4470)\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eIsocyanate\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHDI\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eIPDI\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eDesmodur N3390\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eDesmodur Z4470\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNCO content\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e49.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e37.5\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e19.6\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e11.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e2.7 Characterization\u003c/h2\u003e \u003cp\u003eThe characterization of 1HNMR spectra was recorded on a Bruker Avance operating at a frequency of 300 MHz using tetramethylsilane (TMS) as an internal standard and CDCl3 as solvents. Infrared spectra from 400 to 4000 cm-1 were recorded on a Shimadzu 470 FT-IR instrument, using potassium bromide pellets. Gel permeation chromatography (GPC) was performed on Agilent Tech., Model 1260 infinity equipped with a differential refractometer and mixed column. Tetrahydrofuran (1.0 mL/min) was used as the eluent at 30\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u0026deg;C. Differential scanning calorimetry (DSC) experiments were performed using a TA DSC Q200 calorimeter under a nitrogen atmosphere. The sample was heated to 120\u0026deg;C at a heating rate of 10\u0026deg;C min-1. Gloss was measured at an angle of 45\u0026deg; on a digital glossmeter RSPT-20 by ASTM D2457\u0026ndash;13. The hardness of the coatings was measured by Shore A Zwick Roell by ASTM D 2240. The scratch resistance of the samples was measured using the automatic scratch tester Rajdhani. Acid value of OO, MO, EMO, AMO was measured by ASTM D7253 method. The precision thickness of the coatings was measured by CMI155 HITACHI. The hydroxyl number of Polyol (PAMO) was determined by ASTM D4274 test method D. The isocyanate content of HDI, IPDI, Desmodur N3390, and Desmodur Z4470 was measured by ASTM D2572-97. The adhesion test was performed using a crosscut adhesion tester (model no. 107, elcometer, UK) and ASTM D-3395a.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Synthesis of monomer and polymer\u003c/h2\u003e \u003cp\u003eAs presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the monomer AMO was synthesized from olive oil by methanolysis, epoxidation, and ring-opening reaction. If we directly epoxidize the olive oil and then polymerize it, the polyol would become a gel before forming because the number of double bonds on the monomer would be increased to 3, that is, 3 polymerization sites in one monomer. This is also the reason why we did not use other oils. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e2\u003c/span\u003e, the bio-based acrylic polyol (PAMO) was prepared by solution radical polymerization initiated using AIBN. The transparent thermoset polyurethane coating was obtained by the reaction of bio-based acrylic polyol and isocyanates (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e3\u003c/span\u003e). FTIR, 1HNMR, GPC, viscosity, and hydroxyl number followed the conversion of functional groups. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e4\u003c/span\u003e, the FTIR spectrum of olive oil, MO, EMO, AMO, and PAMO was compared. The peak around 1720 cm-1 is related to the carbonyl group, and the peak at 3008 cm-1 is related to the C-H of the unsaturated band of the oil chains. Comparing the fingerprint region of the MO spectrum with the OO made it possible to find the synthesized MO successfully. In the FTIR spectrum of EMO, the peak of region 3008 cm-1 belonging to the H-C bond attached to the C\u0026thinsp;=\u0026thinsp;C disappeared, and a very low-intensity peak at 830 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e belonging to the (C-O) group was raised in the FTIR of EMO. This is a reason for the complete conversion of the double band to the epoxy group. The reaction of epoxy groups and acrylic acid was confirmed by the appearance of peaks at 810 cm-1, 984 cm-1, 1406 cm-1, and 1635 cm-1 related to the C-H bonds of acrylic groups and the broad peak in 3500\u0026ndash;3700 cm-1 belonged to the H-O bonds. Free radical polymerization of synthesized bio-based monomer initiated by benzoyl peroxide was monitored using FTIR. The peaks related to the acrylic group disappeared.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003e, the chemical structure of the products was confirmed using 1HNMR. The 1HNMR spectrum of olive oil is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003e. The peak area of 0.9 ppm corresponds to the methyl groups at the end of the carbon chain oil, the peak area of 2.1 ppm corresponds to CH2 attached to the carbonyl group, the peak area of 4.6 to 4.8 ppm is related to CH and CH2 on the glycerol and the area 5.8 ppm is related to the double bond hydrogen. With methanolysis reaction, the triglyceride is converted to methyl ester which resulted in the elimination of CH2 and CH peaks attached to ester groups, approving the complete conversion of triglyceride into methyl ester. 1HNMR confirmed the epoxidation of the C\u0026thinsp;=\u0026thinsp;C bond. In the EMO \u003csup\u003e1\u003c/sup\u003eHNMR spectrum, the disappearance of the peak in region 5.8 ppm and the appearance of the peak in region 2.8 ppm corresponding to hydrogen attached to the epoxy ring group indicate the complete conversion of the double bond to the epoxy group. With the ring-opening of the epoxy group by acrylic acid, the peak at 2.9 ppm, which belonged to hydrogen attached to the epoxy group, became invisible. The peaks in the region of 5.75 to 6.5 ppm are related to the C\u0026ndash;H bonds of the unsaturated acrylic group in AMO, and 4.8 ppm are related to C-H bonds attached to the ester group formed from the reaction of acrylic acid and epoxy groups. Finally, the disappearance of peaks at 5.8 to 6.5 ppm confirms that the polymerization of the double bonds of AMO was successfully performed.\u003c/p\u003e \u003cp\u003eThe free radical polymerization of the bio-based monomer to bio-based acrylic polyol was studied using GPC. The GPC chromatogram of PAMO is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e6\u003c/span\u003e. Notably, two peaks of different molecular weights are observed in the PAMO chromatogram. The first pick with a molecular weight of 12712 gr/mol is related to PAMO, and the second pick with a molecular weight of approximately 300 gr/mol and narrow distribution molecular weight is related to the methyl oleate chain, which has no C\u0026thinsp;=\u0026thinsp;C functionality and remains unchanged in the mixture. It is advantageous for a bio-based acrylic coating system that acts as a plasticizer in a polyurethane network. The general specifications of the GPC chromatogram of bio-based PAMO are shown in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Appling theoretical calculations, we can see that the average of monomers in each chain is 33:\u003c/p\u003e\u003cp\u003e\u003cimg src=\"data:image/png;base64,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\"\u003e\u003cbr\u003e\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eGPC data of PAMO\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"2\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e12712 g/mol\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMw\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e30678/mol\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMz\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e87637/mol\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePDI\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.413\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003ewhere DP denotes the degree of polymerization, m signifies the molecular weight of the monomer, and Mn symbolizes the average molecular weight of the polymer chain. The polydispersity index (PDI) of polymerization was approximately 2.4. This is acceptable because of the radical polymerization method. There are many chain transfer reactions in solution radical polymerization, such as chain transfer to solvent, chain transfer to monomer, chain transfer to the polymer chain, etc., that make PDI increase.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Preparation of the transparent polyurethane coating\u003c/h2\u003e \u003cp\u003eFour types of polyurethane were prepared by PAMO reaction with HDI, IPDI, Desmodur N3390, and Desmodur Z4470 in different NCO/OH ratios as summarized in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. Based on the study, the selected isocyanates due to the unique properties of aliphatic polyurethane coating are most suitable for synthesized bio-based acrylic polyol. The chemical structure of the isocyanates is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e7\u003c/span\u003e. The IPDI and HDI are difunctional isocyanates and Desmodur N3390 and Desmodur Z4470 are trifunctional isocyanates. The prepared polyurethanes coating with Desmodur N3390 and Desmodur Z4470 have more cross-linking than HDI and IPDI. The resistance of a polymer to the penetration of a hard object is called the hardness of a polymer. It is notable that if the polyol parameters remain constant, the hardness and scratch resistance of the coating is changed by the isocyanate as follows:\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCoating properties of prepared polyurethane with different isocyanate\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003esample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eIsocyanate\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHardness Shore A\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eGloss\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eScratch resistance (gr)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eCrosscut adhesion\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePU-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHDI\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e59\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e200\u0026ndash;250\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e29\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePU-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eIPDI\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e88\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e200\u0026ndash;250\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePU-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eDesmodur N3390\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e67\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e250\u0026ndash;300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e28\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePU-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eDesmodur Z4470\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e76\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e93\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e300\u0026ndash;350\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eDesmodur Z4470\u0026thinsp;\u0026gt;\u0026thinsp;Desmodur N3390\u0026thinsp;\u0026gt;\u0026thinsp;IPDI\u0026thinsp;\u0026gt;\u0026thinsp;HDI\u003c/p\u003e \u003cp\u003eThis trend can be attributed to the higher functionality of Desmodur Z4470 and Desmodur N3390, which cause higher crosslinking of the coating and the existence of aliphatic and isocyanurate rings in Desmodur Z4470. The presence of isocyanurate and aliphatic rings increases the hardness and scratch resistance of the polyurethane coating. The above trend can be interpreted according to the structure of these isocyanates, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe gloss of the coatings does not change much with the change in the isocyanates. All bio-based polyurethane coatings exhibit excellent gloss. As one of the characteristics of polyacrylic polyols is the high gloss of their coatings, it can be concluded that the high gloss of these coatings is related to the bio-based synthesized polyol. The dangling chains on the polymer backbone seem to be the origin of high glossiness. The mobile dangle chain prevents the close packing of the urethane groups. One of the notable features of the prepared polyurethane coatings is transparency as well as gloss Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e8\u003c/span\u003e. Gloss is an optical property of coatings. As the light beams reach the surface of the coating, some beams pass through the coating. Part of these light beams is reflected and partly diffused. The gloss of a coating depends on how much light the reflection reflects and how much light is diffused. On the other hand, the transparency of the coating depends on the amount of light that passes through the polymer chain of coatings. In the prepared polyurethane coatings, dangling chains of oil cause the polymer chains to move away from each other so the light beam will pass through them. The prepared polyurethanes' adhesion to metal surfaces was studied. All samples indicated excellent adhesion to the surface due to the presence of the ester group of the polyol and urethane groups. It was observed that the metal adhesion properties of sample 3 were higher than those of samples 1 and 2. It seemed the higher adhesion was raised from the isocyanurate ring on Desmodur z4470. It was found that the coating properties of sample 3 proved better than those of samples 1 and 2. Three polyurethane coatings with different NCO/OH (0.9, 1, and 1.2) ratios were prepared. The coating properties of prepared bio-based polyurethanes were measured; the results are listed in Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The hardness and scratch resistance increase with increasing amounts of NCO/OH. As NCO/OH increases from 0.9 to 1, the urethane groups increase, resulting in increased hardness and scratch resistance. When the NCO/OH ratio changes from 1 to 1.2, the excess NCO groups react with air humidity and form urea groups, which increase the crosslink density and hardness and scratch resistance (Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e9\u003c/span\u003e). Increasing the crosslink density results in forming a smooth surface, increasing light reflection, and improving the brightness of the coatings. It is also observed that in 1.2 NCO/OH ratio, the adhesion to the metal increases. The urea groups are likely to increase the adhesion of the coating to the metal. The glass transition temperatures (Tg) and the melting point of the prepared polyurethane coating were determined after the second scan, which are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e10\u003c/span\u003e. The DSC spectra were obtained from three polyurethane coatings Pu-3-1, Pu-3-2, and Pu-3-3 made from PAMO and Desmodur Z4470. The resulting bio-based polyurethane network is three-dimensional because the designed biobased polyol is highly functional, and it appears that all the crosslinks are not covalent bands and some of them are hydrogen bands. It means that urethane and urea linkages are enhanced with an increase in NCO/ OH ratio, leading to more cross-linking densities that limit the polymer mobility. As NCO/OH ratios affect the thermal and mechanical behaviors of the polyurethane coating, the Tg values and the thermal properties of the prepared samples are influenced by the NCO/OH ratio as well. As the NCO/OH ratio increases from 0.9 to 1.2 molar ratio, the Tg values increases from 54 to 85\u0026deg;C, respectively. It seems transfer in region 129\u0026deg;C is related to the separation of the urethane-urethane hydrogen bonds and temperature transfer above 199 \u0026deg; C is related to the heat degradation of polyurethane.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCoating properties of prepared polyurethane with different NCO/OH\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003esample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eNCO/OH\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHardness Shore A\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eGloss\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eScratch resistance (gr)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eCrosscut adhesion\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePu-4-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e65\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e250\u0026ndash;300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e22\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePu-4-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e73\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e93\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e300\u0026ndash;350\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e22\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePu- 4\u0026thinsp;\u0026minus;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e300\u0026ndash;350\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e17\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn conclusion, we designed and synthesized novel bio-based polyacrylic polyols and explored their coating properties for transparent and glossy polyurethane coating. In the first step, polyacrylic polyol was successfully synthesized by methanolysis of olive oil, epoxidation of the double bond, and oxirane ring-opening by acrylic acid. In the second step, the monomer was polymerized by solvent radical polymerization. The chemical structure of intermediates and polyol was verified by FT-IR, 1HNMR, and GPC. The obtained polyacrylic polyol reacted with four types of isocyanates (HDI, IPDI, Desmodur N3390, and Desmodur Z4470) and polyurethane coatings. Considering that the best results were obtained from Desmodur Z4470, we synthesized three NCO/OH ratios from PAMO and Desmodur Z4470, and evaluated their physical properties. The best results were obtained with the PAMO polyol and the Desmodur Z4470 isocyanate with a ratio of 1.2. The results show that it is possible to actuate olive oil based polyacrylic polyol to produce a unique and useful material. In other words, the prepared bio-based polyurethanes with high gloss are usable as transparent films and are important in the coating industry.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eConflict of Interest\u003c/h2\u003e \u003cp\u003e \u003cb\u003eThe authors declare no conflicts of interest.\u003c/b\u003e \u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eAuthor ContributionsEhsan Salarvand fed the data to the software, carried out the analysis, wrote the original draft and the methodology. Ismail Omrani undertook the conceptualization, project administration, and writing - the original draft. Milad Salehi embarked on the review and editing. Mohammad Reza Nabid pursued the funding acquisition and investigation.\u003c/p\u003e\u003ch2\u003eData Availability Statement\u003c/h2\u003e \u003cp\u003eData available on request from the authors\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eGogoi R, Niyogi UK, Alam MS, Mehra DS (2013) Study of effect of NCO/OH molar ratio and molecular weight of polyol on the physico-mechanical properties of polyurethane plaster cast. World Appl Sci J 21:276\u0026ndash;283\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKugel AJ, Jarabek LE, Daniels JW et al (2009) Combinatorial materials research applied to the development of new surface coatings XII: Novel, environmentally friendly antimicrobial coatings derived from biocide-functional acrylic polyols and isocyanates. J Coat Technol Res 6:107\u0026ndash;121\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eOmrani I, Babanejad N, Shendi HK, Nabid MR (2017) Preparation and evaluation of a novel sunflower oil-based waterborne polyurethane nanoparticles for sustained delivery of hydrophobic drug. Eur J Lipid Sci Technol 119:1600283\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMoghadam PN, Yarmohamadi M, Hasanzadeh R, Nuri S (2016) Preparation of polyurethane wood adhesives by polyols formulated with polyester polyols based on castor oil. Int J Adhes Adhes 68:273\u0026ndash;282\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCakić SM, Ristić IS, Milena M et al (2016) Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly (ethylene terephthalate) waste. Int J Adhes Adhes 70:329\u0026ndash;341\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCzłonka S, Bertino MF, Kośny J et al (2018) Linseed oil as a natural modifier of rigid polyurethane foams. Ind Crops Prod 115:40\u0026ndash;51\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePinto ML (2010) Formulation, preparation, and characterization of polyurethane foams. J Chem Educ 87:212\u0026ndash;215\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eShen D, Shi S, Xu T et al (2018) Development of shape memory polyurethane based sealant for concrete pavement. Constr Build Mater 174:474\u0026ndash;483\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDing H, Wang J, Wang C, Chu F (2016) Synthesis of a novel phosphorus and nitrogen-containing bio-based polyols and its application in flame retardant polyurethane sealant. Polym Degrad Stab 124:43\u0026ndash;50\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYeganeh H, Talemi PH, Jamshidi S (2007) Novel method for preparation of polyurethane elastomers with improved thermal stability and electrical insulating properties. J Appl Polym Sci 103:1776\u0026ndash;1785\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGang H, Lee D, Choi K-Y et al (2017) Development of high performance polyurethane elastomers using vanillin-based green polyol chain extender originating from lignocellulosic biomass. ACS Sustain Chem Eng 5:4582\u0026ndash;4588\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCampanella A, Bonnaillie LM, Wool RP (2009) Polyurethane foams from soyoil-based polyols. 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J Polym Sci Polym Chem 44:634\u0026ndash;645\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJunming X, Jianchun J, Jing L (2012) Preparation of polyester polyols from unsaturated fatty acid. J Appl Polym Sci 126:1377\u0026ndash;1384\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"acrylic polyol, transparent polyurethane coating, renewable polyol","lastPublishedDoi":"10.21203/rs.3.rs-4620993/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4620993/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTo prepare a transparent polyurethane coating, a renewable, green, and scalable polyacrylic polyol (PAMO) was synthesized from olive oil (OO) and applied as a polyol. To prepare PAMO, the olive oil was first methanolized using methanol, and methyl oleate (MO) was obtained, followed by its getting epoxidized by formic acid and hydrogen peroxide. Epoxidized methyl oleate (EMO) was ring-opened using acrylic acid (AA) with excellent yield. Further, to prepare PAMO, radical polymerization method was utilized. FT-IR, \u003csup\u003e1\u003c/sup\u003eHNMR, and gel permeation chromatography (GPC) verified the chemical structures of the synthesized monomer and polymer. Different thermoset aliphatic transparent polyurethane coatings were obtained by reacting the synthesized polyol with hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), Desmodur N3390, and Desmodur Z4470. The best results were obtained using Desmodur Z4470 as the curing agent. Polyurethane obtained from PAMO and Desmodur Z4470 was acquired in three NCO/OH ratios of 0.9, 1, and 1.2, with the 1.2 NCO/OH ratio as the best-obtained result. The new polyol architecture has emerged as a new polyacrylic polyol and transparent polyurethane coatings class.\u003c/p\u003e","manuscriptTitle":"A Renewable, Green, and Scalable Polyacrylic Polyol (PAMO) Derived from Olive Oil for Transparent Polyurethane Coatings","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-15 12:10:31","doi":"10.21203/rs.3.rs-4620993/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"b9813785-0a3a-4783-be27-149a45dff978","owner":[],"postedDate":"July 15th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-08-13T07:29:57+00:00","versionOfRecord":[],"versionCreatedAt":"2024-07-15 12:10:31","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4620993","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4620993","identity":"rs-4620993","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}