Effective Studies of bio-derived free radical polymerizable hydroxyl functional Macromonomer for replacement of Hydroxyl Ethyl Methacrylate (HEMA) in acrylic polyols and their Polyurethane-Urea Coatings

Effective Studies of bio-derived free radical polymerizable hydroxyl functional Macromonomer for replacement of Hydroxyl Ethyl Methacrylate (HEMA) in acrylic polyols and their Polyurethane-Urea 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 Effective Studies of bio-derived free radical polymerizable hydroxyl functional Macromonomer for replacement of Hydroxyl Ethyl Methacrylate (HEMA) in acrylic polyols and their Polyurethane-Urea Coatings ALLAUDDIN SHAIK, Kiran Kumar Nehete, Subarna Shyamroy This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5260042/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 15 Feb, 2025 Read the published version in Journal of Polymer Research → Version 1 posted 5 You are reading this latest preprint version Abstract The present work to study the impact of substituting the HEMA monomer in the synthesis of acrylic polyols with a bio-based free radical hydroxyl functional macromonomer derived from castor oil (CO). It also evaluates the coating properties of the resulting polyurethanes (PUs) in comparison to conventional acrylic polyols (AP-HEMA) derived from HEMA. To achieve this, castor oil was first reacted with maleic anhydride (MA) to produce the castor oil-derived free radical polymerizable hydroxyl functional macromonomer (COMA). Subsequently, castor oil-based acrylic hybrid polyols were synthesized using acrylate monomers, specifically methyl methacrylate (MMA) and butyl acrylate (BA), along with varying weight percentages of COMA through a conventional radical copolymerization process. The successful replacement of HEMA with COMA in the acrylic polymerization was confirmed through Fourier transform infrared (FTIR) spectroscopy, hydroxyl value analysis, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The acrylic hybrid polyols derived from castor oil exhibit reduced viscosity, lower glass transition temperature (Tg), and diminished molecular weight when compared to AP-HEMA. Both types of resins, namely the castor oil-based and AP-HEMA, underwent further reaction with Isophorone diisocyanate (IPDI) at an OH: NCO ratio of 1:1.6, resulting in isocyanate-terminated polyurethane pre-polymers. The Tg of the castor oil-based acrylic hybrid polyurethane coating films was observed to be lower than that of petroleum-derived HEMA-based acrylic polyols, demonstrating enhanced performance in terms of contact angle, water resistance, flexibility, adhesion, and abrasion resistance. The overall findings suggest that the bio-derived free radical polymerizable hydroxyl functionality possesses a polymerization tendency within the conventional acrylic polymerization framework, indicating its potential as a substitute for the HEMA monomer in the synthesis of acrylic polyols, thereby yielding high solid content resins suitable for high-performance polyurethane coating applications. castor oil maleic anhydride polyurethane swelling glass transition thermal Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 1. Introduction Recent trends in industry and literature have highlighted the growing necessity for awareness regarding sustainable development platforms. This shift aims to foster the creation of environmentally friendly functional macromers and polymers, as well as to substitute petroleum-based components and polymer materials with those derived from renewable resources. 1 – 2 In particular, the use of agricultural feedstocks, such as plant oils, is gaining traction as a sustainable approach to developing environmentally friendly materials and polymers. This shift aims to replace existing petroleum-based monomers and polymers, focusing on both cost-effectiveness and performance attributes. 3 – 5 Plant oils are vital components in the synthesis of bio-based polymers that demonstrate superior performance. Among these oils, castor oil is particularly advantageous as a bio-based polyol, given its natural hydroxyl functionalities. This characteristic allows for its direct incorporation into polyurethane production, resulting in improved gloss, flexibility, and water resistance. 6 – 7 The synthesized polyurethane materials derived from plant oils exhibit limited mechanical strength, stiffness, and thermal stability. These characteristics are essential for high-performance structural applications. 8 – 9 However, the inherent chemical structure of plant oils contains non-conjugated carbon–carbon double bonds, which lack the reactivity necessary to promote free radical polymerization effectively. 10 Hence, the functionalization of plant oils is vital for their use as core building blocks in bio-based polymers. It is a well-established reality that a plant oil feedstock is being created for blending or structural modifications in a range of coating applications. 11 – 12 The unsaturation present in plant oils exhibits low reactivity in terms of polymerization and chemical modification, necessitating elevated temperature conditions. 13 – 15 As a significant renewable resource, natural plant oils have been utilized to develop bio-based UV curable materials through a variety of chemical methods. 16 – 19 The incorporation of functional reactive sites within plant oils, as well as the presence of renewable constituents with appropriate active unsaturation functionalities for polymerization, remains an encouraging development. However, there is a need for further progress in utilizing these modified plant oils in acrylic polymerization. The present research is designed to showcase the feasibility of a bio-derived free radical polymerizable hydroxyl functional macro-monomer in the conventional acrylation process. It also aims to compare the physical and coating properties of the resulting polyurethanes (PUs) with those of acrylic polyols (AP-HEMA) produced from the same conventional acrylate monomers, including Methyl methacrylate (MMA) and Butyl acrylate (BA), along with a commercially available petroleum-derived acrylate hydroxyl functionality, HEMA. Thus, the focus of this research is on evaluating the effectiveness of replacing HEMA in the conventional acrylation process with a free radical polymerizable hydroxyl functional macromonomer (COMA) obtained from castor oil. 2. Experimental section 2.1. Materials. Castor oil (CO) was sourced from the commercial market, exhibiting characteristic properties with a hydroxyl value ranging from 162 to 165 mg KOH/g and an acid value below 2 mg KOH/g. Isophorone diisocyanate (IPDI) was acquired from Evonik Industries in Germany. All acrylic monomers, including methyl methacrylate (MMA), butyl acrylate (BA), and hydroxyl ethyl methacrylate (HEMA), were obtained from various commercial suppliers. The initiator, Di-tert-butyl peroxide (DTBP), was procured from Luperox and is of analytical grade. Maleic anhydride (MA), dibutyltin dilaurate (DBTDL), and other chemicals were also of analytical grade and utilized without additional purification. 2.2. Synthesis of bio derived free radical polymerizable hydroxyl functionality macro monomer (COMA). The Adduct (COMA) was synthesized from 100 grams of castor oil and 4 grams of maleic anhydride utilizing a four-neck round-bottom flask fitted with a mechanical stirrer, nitrogen purge, and thermometer, with the reaction conducted at a temperature of 90°C. The progress of the anhydride ring-opening reaction involving maleic anhydride and castor oil was tracked using an FT-IR spectrophotometer, observing the disappearance of the anhydride peak at 1850 cm − 1 in the final spectra. The modified castor oil, which possesses free radical polymerizable hydroxyl functionality, is referred to as COMA throughout this manuscript. The schematic representation of COMA is illustrated in Scheme 1 . 2.3. Synthesis of Acrylic Polyol using HEMA (AP-HEMA). AP-HEMA was synthesized via the solution polymerization of acrylate monomers in butyl acetate solvent. The butyl acetate was placed in a four-necked flask equipped with a thermometer, condenser, and motor-driven stirrer. Separately, a mixture of the monomers MMA, BA, and HEMA, along with 1.4 g of the initiator DTBP, was prepared in a round-bottom flask. The monomer mixture was introduced into the system using a peristaltic pump over a duration of three hours at a temperature of 120°C. An additional 0.2 g of DTBP was then added, and the polymerization process continued for an additional hour at the same temperature to ensure complete conversion. The resulting acrylic polyol was designated as AP-HEMA, with a hydroxyl value of 93.64 mg KOH/g. 2.4. Synthesis of Bio based Acrylic Hybrid Polyols using COMA. Four experimental bio-based acrylic hybrid polyols were synthesized utilizing varying weight ratios of COMA while maintaining constant weight ratios of acrylate in the acrylation process. The weight amounts of the different raw materials employed in the reaction are presented in Table 1 . A similar procedure was followed for the acrylation of COMA. Butyl acetate solvent was utilized in a four-necked flask equipped with a thermometer, condenser, and motor-driven stirrer. A separate mixture of the monomers MMA, BA, and COMA, along with 1.4 g of the initiator DTBP, was prepared in a round-bottom flask. The monomer mixture was introduced into the system via a peristaltic pump over a duration of three hours at a temperature of 120°C. An additional 0.2 g of DTBP was incorporated into the system, and the polymerization reaction was allowed to proceed for an additional hour at the same temperature to ensure complete conversion. The acrylic polyols derived from COMA are designated as AP-CO-1, AP-CO-2, AP-CO-3, and AP-CO-4. Notably, only AP-CO-3 exhibits a hydroxyl value that is comparable to that of AP-HEMA. Digital images of the resulting bio-based acrylic hybrid polyol binders are illustrated in Fig. 1 . The bio content, specifically the castor oil content, in each formulation was calculated based on 100 parts by weight of the total formulation, as detailed in Table 1 , with a solid content of 50% maintained across all binder formulations. The properties of the synthesized polyols are summarized in Table 2 , while Scheme 1 provides a schematic representation of the structure and process of the bio-based acrylic hybrid polyol. Table 1 Various weight ratios (in grams) used to prepare the bio based acrylic hybrid polyols. Sample code MA CO MMA BA HEMA COMA CO:Acrylate ( %) COMA 4 100 - - - - - AP-HEMA - - 20 21 9 - - APCO-1 20 21 - 24 37:63 APCO-2 20 21 - 49 54:46 APCO-3 20 21 - 79 66:34 APCO-4 20 21 - 158 80:20 Table 2 Mole ratios used to prepare the different 2K PU coatings. Sample code IPDI(OH:NCO) COPU 1:1.6 AP-HEMA-PU 1:1.6 AP-COPU-1 1:1.6 AP-COPU-2 1:1.6 AP-COPU-3 1:1.6 AP-COPU-4 1:1.6 2.5. Synthesis of Polyurethane-Urea coating films. The synthesized polyols were subsequently reacted with IPDI at an NCO:OH ratio of 1.6:1 at approximately 80°C to produce –NCO terminated polyurethane pre-polymers. These pre-polymers were then applied onto releasing paper using a manually operated square film applicator to achieve uniform final coating films. The –NCO terminated pre-polymer was exposed to atmospheric moisture and laboratory humidity for a duration of 15 days to facilitate moisture curing. The complete curing of the films was indicated by the disappearance of the –NCO peak at 2270 cm − 1 in the FT-IR spectroscopy analysis. The polyurethanes derived from AP-CO-1, AP-CO-2, AP-CO-3, and AP-CO-4 were designated as AP-COPU-1, AP-COPU-2, AP-COPU-3, and AP-COPU-4, respectively, while the polyurethane from AP-HEMA was labeled as AP-HEMA-PU. For reference and comparison, a castor oil-based polyurethane was synthesized using solely castor oil (CO) and was designated as COPU. The compositions of the various polyurethanes are detailed in Table 2 . Digital images of the resulting bio-based polyurethane films, which have a thickness of 150 µm, are presented in Fig. 2 . 3. Results and Discussion 3. 1. Effect of structural variation on molecular weight, viscosity, and glass transition temperature The characterization of acrylic polyols, CO, and their pre-polymers was conducted utilizing gel permeation chromatography on a Varian ProStar chromatograph model-210 from the USA. A sample concentration of 0.1 g per 10 mL was prepared by dissolving the samples in THF, and the experiments were performed at a flow rate of 1.0 mL/min with THF serving as the mobile phase. Calibration of the columns was achieved using Aldrich polystyrene standards. The polymerization of the COMA backbone with MMA and BA significantly influenced the molecular weight, viscosity, and glass transition temperature in comparison to unmodified castor oil. Scheme 1 illustrates the schematic steps involved in the synthesis of bio-based acrylic hybrid polyols and their corresponding polyurethanes, while Table 3 presents the physical characteristics of the pre-polymers and various monomer reactants utilized in the synthesis of the bio-based acrylic hybrid polyols, along with their respective weight ratios. The analysis of molecular weights (Mw) was conducted through the GPC technique utilizing tetrahydrofuran as the solvent, with the findings presented in Table 3 . The variation in weight ratios of COMA has resulted in an increase in molecular weight, which can be attributed to the development of an acrylic network. Upon reviewing the GPC data, it is evident that the Mw and Mn of bio-based hybrid polyols are superior to those of CO and COMA. This enhancement is a result of the polymerization involving MMA and BA with the bio-derived free radical polymerizable hydroxyl functionality macromonomer (COMA), which is considerably less reactive than the petroleum-derived HEMA. As a result, the molecular weight of AP-HEMA is greater than that of the bio-based acrylic hybrid polyols. Additionally, the viscosities of the bio-based hybrid polyols, measured at 50% solid content and 27.4°C using the ICI cone and plate viscometer VR-4410 at 900 RPM, were observed to be higher than those of COMA and CO. This increase in viscosity is expected due to the radical polymerization process, as shown in Table 3 . The dominance of higher molecular weight polymers leads to increased viscosity, which can be attributed to the polymerization process occurring in AP-HEMA. The glass transition temperature characteristics of CO, COMA, and their acrylic polyols, along with AP-HEMA, were examined using Differential Scanning Calorimetry (DSC) on a TAQ 2000 (TA Instruments, USA). The samples were subjected to heating from − 70 to 150°C at a rate of 10°C/min in a nitrogen atmosphere with a flow rate of 30 mL/min, and the data is presented in Table 3 . This finding further substantiates that the acrylic grafting of COMA with MMA and BA acrylates occurred through radical polymerization, resulting in an increase in the Tg of the binders. Table 3 Characteristics of different binders. Sample ID Mn (gm/mol) Mw (gm/mol) Mz (gm/mol) P.D.I OH value Viscosity (cps) Tg 0 C CO 1227 1384 1471 1.12 165.48 640 -30.68 COMA 1359 1539 1676 1.13 136.5 890 -28.8 AP-HEMA 12305 47603 114840 3.86 93.64 6000 8.4 AP-CO-1 3493 17808 59246 3.09 73.28 2300 1.8 AP-CO-2 2192 7889 28939 3.59 82.3 1300 1.4 AP-CO-3 1982 6273 22192 3.16 90.85 900 0.9 AP-CO-4 1837 3732 8859 2.03 105.21 800 0.4 3.2. FTIR analysis of the hybrid polyols and their PU-Urea films The chemical structures of acrylic polyols, oils, and their hybrid polyols, along with their polyurethane films, were analyzed using Fourier transform infrared spectroscopy (FTIR) on a PerkinElmer Spectrum One instrument. The structural characteristics of both modified and unmodified castor oil were examined through FTIR. The FT-IR spectra for castor oil, COMA, and its acrylic hybrid, as well as AP-HEAM polyol, are presented in Fig. 3 . In the case of castor oil, a broad peak at 3454 cm − 1 corresponds to the absorption of the -OH functional group, while the stretching frequency of the -HC = CH- double bond is observed at 1640 cm − 1 . Notably, no peaks associated with the cyclic anhydride group at 1779 cm − 1 and 1849 cm − 1 were detected in COMA, suggesting that the anhydride ring was consumed during the reaction with castor oil. Consequently, the newly formed unsaturation in the COMA spectra is indicated by the absorption peak at 1640 cm − 1 , [20] which can be attributed to the stretching frequency of the –HC = CH– double bond. When castor oil reacts with MA, a significant reduction in the -OH peak is observed, while the peak corresponding to the double bond is notably enhanced. The peaks observed at 1385 cm − 1 and within the range of 2800–3000 cm − 1 are attributed to the bending of –C–H bonds from the terminal methyl group and the aliphatic –C–H bonds, respectively. This suggests that the integration of acid functionality into the castor oil backbone was effectively achieved through the ring-opening reaction of the anhydride with the secondary hydroxyl group present in castor oil. The corresponding acrylic grafting of COMA and AP-HEMA is illustrated in Fig. 3 . In this figure, AP-HEMA displays an –OH stretching at 3532 cm − 1 (broad band), >C = O stretching (acrylic ester) at 1732 cm − 1 , –CH 2 stretching at 2957 cm − 1 , –C–H bending at 1452 cm − 1 and 1387 cm − 1 , as well as C–O stretching (acrylic) at 1072 cm − 1 and 1167 cm − 1 . The incorporation of COMA into MMA and BA resulted in the disappearance of the intensity peak around 1697 cm − 1 , indicating that the unsaturation of MA underwent polymerization with acrylates. The FT-IR spectra of the polyurethane coating films are presented in Fig. 4 and exhibit notable similarities. Characteristic absorption bands include the –N–H stretching observed between 3500 − 3300 cm − 1 , the urethane carbonyl associated with ─NH–CO–O (alongside secondary amide peaks) and ─CO─O (ester carbonyl) within the range of 1740 − 1728 cm − 1 , as well as a combination of ─C–N and ─N–H out-of-plane bending stretching at 1525 cm − 1 , which are evident across all spectra. The absorbance features in the spectra of the polyurethane coating films, derived from bio-based acrylic hybrid polyols, indicate the presence of castor oil-derived polymeric films, characterized by the stretching vibrations of the aliphatic ─CH 2 groups at 2925 and 2855 cm − 1 , and the –CH 2 bending vibrations at 1385 cm − 1 [21]. 3.3. DMA analysis of the hybrid films Thermal analysis was conducted using a dynamic mechanical analysis (DMA) TAQ800 instrument from TA Instruments, USA, operating in tensile mode at a frequency of 1 Hz and a heating rate of 3°C/min. The films were scanned over a temperature range from − 60 to 150°C. The viscoelastic properties of the coating films were examined with the DMA equipment, yielding results for the tensile storage modulus (E′), the corresponding loss modulus (E″), and the loss factor tan δ, which is defined as the ratio of the loss modulus to the storage modulus, E″/E′. The glass transition temperature (Tg) values of the PU-urea films were determined from the peaks observed in the tan δ curves. Additionally, the crosslink density (υe) of the films was calculated using the formula provided below. υe = E′ / 3RT Where R is the universal gas constant, and T the temperature in K. E′ values in the rubbery region at T > Tg were taken to calculate υe by using above formula. Figures 5 and 6 illustrate the relationship between E′, E″, and tan δ as a function of temperature (T), with the dynamic properties of the films represented in the accompanying curves. The data is consolidated in Table 4 . The DMA curves of the films exhibit characteristics akin to homogeneous polymeric networks concerning the storage modulus (E′) curves. Notably, AP-HEMA-PU demonstrates superior E′ and Tg values when compared to COPU and other bio-based acrylic hybrid PUs; however, the crosslink density of the coating films is influenced by the hydroxyl values of the resins. The Tg values for COPU, AP-HEMAPU, AP-COPU-1, AP-COPU-2, AP-COPU-3, and AP-COPU-4 are recorded as 27.21, 79, 29.7, 28, 26, and 21.4°C, respectively. At 20°C, the E′ values for COPU, AP-HEMAPU, AP-COPU-1, AP-COPU-2, AP-COPU-3, and AP-COPU-4 hybrid coating films are 6.4 x 10 7 , 1.24 x 10 9 , 3.08 x 10 7 , 2.41 x 10 7 , and 2.52 x 10 7 Pa, respectively. In the rubbery region at Tg + 5°C and Tg + 30°C, an increase in OH functionality due to a higher percentage of oil incorporation results in AP-COPU-4 exhibiting a greater storage modulus, followed by AP-COPU-3, AP-COPU-2, and AP-COPU-1. This is attributed to the higher hydroxyl functionality leading to increased crosslink density compared to other bio-based acrylic hybrid PUs, which may enhance the mechanical properties of AP-COPU-4. Furthermore, based on the DMA Tg data, it is possible to enhance the Tg of bio-based acrylic hybrid PUs by selecting monomers according to their Tg and the ratio of COMA to acrylate, achieving results comparable to conventional petroleum-derived HEMA-based acrylic polyols. [22–23] Table 4 DMA data of the different 2K PU coatings. Sample ID Tg(°C) Tan δmax E′ at 20°C [Pa] E′ at Tg + 5°C [Pa] E′ at Tg + 30°C [Pa] υ e (Tg + 5°C) (mole/cm 3 ) COPU 27.2 0.78 6.4 x 10 7 1.8 x 10 7 3.7 x 10 6 2.36 x 10 − 3 AP-HEMA-PU 79.4 0.64 1.24 x 10 9 1.04 x 10 7 3.8 x 10 6 1.16 x 10 − 3 AP-COPU-1 29.7 1.33 3.08 x 10 7 0.8 x 10 7 1.2 x 10 6 1.04 x 10 − 3 AP-COPU-2 28.0 1.11 2.41 x 10 7 0.6 x 10 7 1.1 x 10 6 0.78 x 10 − 3 AP-COPU-3 26.0 0.98 3.15 x 10 7 1 x 10 7 1.52 x 10 6 1.31 x 10 − 3 AP-COPU-4 21.4 0.99 2.52 x 10 7 1.3 x 10 7 2.41 x 10 6 1.74 x 10 − 3 3.4. Contact angle of the hybrid films The contact angle was assessed using the DSA 100 (KRUSS) instrument via the sessile drop method. Measurements of the contact angle (CA) were conducted on the films with water and ethylene glycol serving as probe liquids. The resulting surface free energies (SFE) and contact angle data are compiled in Table 5 . The COPU and bio-based acrylic hybrid polyols exhibit superior hydrophobic characteristics compared to the AP-HEMA-PU coatings. Specifically, the AP-HEMA-PU demonstrates a lower water CA of approximately 68.5°, while the bio-based acrylic hybrid PU surfaces show water CAs ranging from 75.4° to 80.5°, and the COPU presents a water CA of about 81.9°. The enhancement in water contact angle for the bio-based hybrid PU can be attributed to the grafting of COMA in the acrylate monomers, which improves the hydrophobic properties of the bio-based hybrid coating by increasing the weight ratio of COMA during acrylation, leading to the formation of fatty acid chains through the incorporation process. Similar oleophobic properties were observed with ethylene glycol. Table 5 Contact angle data of the different 2K PU coatings. Sample code Contact angle (Ɵ) SFE (mN/m) Water Ethylene glycol AP-HEMA 68.56 57.31 52.6 AP-CO-1 75.47 59.10 47.7 AP-CO-2 76.48 61.85 44.7 AP-CO-3 78.53 63.40 42.3 AP-CO-4 80.52 66.78 41.8 CO-PU 81.94 68.54 40.1 3.5. Swelling properties of the films Table 6 also shows the water and toluene swelling as a function of immersion time (72 hr) of the films. The swelling ratio (Q %) in water is calculated using following equation [22] . Table 6 Swelling properties of different 2K PU coatings. Film samples Q % (water) Q L % (water) W t % (Toluene) W L % (Toluene) CO-PU 0.6 0.65 136.2 3.2 AP-HEMA-PU 1.8 3.87 60.1 12.1 AP-COPU-1 1.3 1.97 253.6 28.6 AP-COPU-2 1.1 1.85 236.5 24.5 AP-COPU-3 1 1.34 214.7 17.2 AP-COPU-4 0.75 1.10 167.1 10.8 Swelling ratio (Q), % = [(W s − W d )/W d ] × 100 Amounts of the films dissolved into the water: (Q L ) % = [(W d -W od )/W d ] x 100 Where W d is the weight of the dry sample as such and W s is the weight of the swollen sample. W od is the weight of oven dried sample. In toluene, calculation was done according to the following equations. W t (%) = [(W 1 – W 0 )/W 2 ] × 100 W t : amounts of toluene absorption by the film. W L (%) = [(W 0 − W 2 )/W 0 ] × 100 W L : amounts of the films dissolved into the toluene solution. Where known weight (W 0 ) of the films, the towel down dry sample weight (W 1 ) and the oven-dried sample weight (W 2 ) were obtained. All films demonstrated considerable swelling in toluene solvent, as illustrated in Table 6 . The data from the overall swelling studies indicate that the bio-based hybrid polyurethane coating films exhibit lower solvent resistance but higher water resistance when compared to AP-HEMA-PU coatings. The inclusion of COMA generally reduced the degree of swelling, suggesting that the addition of fatty hydrocarbon chain networks within the castor oil backbone may be responsible for this effect. This phenomenon can be attributed to the expected characteristics of the network model, as well as the asymmetrical chemical structures present in the bio-based hybrid acrylic polyurethane films [24]. 3.6. TGA analysis of the hybrid films Thermogravimetric analysis was performed using a Mettler Toledo TGA 1/SDTAe apparatus, with a heating rate set at 10°C per minute in a nitrogen atmosphere. The thermal degradation profiles of PU-Urea films are illustrated in Fig. 7 . The volatilization of residual solvents and trapped moisture within the coating films occurs during decomposition at temperatures ranging from 100 to 150°C. Studies on oil-based PU-urea coating films reveal three distinct decomposition stages. [ 25–26] In the initial stage, PU exhibits a gradual decomposition up to 335°C, resulting in a weight loss of 30–43%. The TGA curves for COPU and bio-based acrylic hybrid PU indicate that the primary degradation process occurs between 350°C and 365°C, while AP-HEMA-PU shows degradation at temperatures between 370°C and 420°C. A summary of the comparative TGA data, including Ton (initial decomposition temperature), Tend (final decomposition temperature), Tmax (maximum decomposition temperature), and percentage weight remaining at 250°C, 350°C, and 450°C, is presented in Table 7 . The data indicate that the thermal stability of the PU coating films improves with increased oil content, suggesting that higher unsaturation levels necessitate additional thermal energy to break down the extra bonds prior to complete network degradation. [ 27–28] This behavior may be influenced by the network structure and various chemical structural factors, including steric strain and the conformational arrangements of the groups. The TGA curves and corresponding data suggest that the thermal stability of the bio-based acrylic hybrid films surpasses that of the AP-HEMA-PU. Table 7 TGA data of different 2K PU coatings. Sample ID T on ( o C) T max ( o C) T end ( o C) %weight remaining at T max 1 T max 2 T max 3 250 o C 350 o C 450 o C COPU 242 320 356 410 469 99.3 56.6 4.3 AP-HEMA-PU 256 - 370 415 453 93.1 73.4 1.5 AP-COPU-1 250 305 325 403 466 97.4 76.7 4.5 AP-COPU-2 248 307 325.7 406 469 96.9 71.3 7.6 AP-COPU-3 246 326 365 405 469 97.5 69.2 7.3 AP-COPU-4 232 318 362 411 472 96.7 68.2 10.4 3.7. Tensile, Adhesion, Abrasion, Hardness, Scratch, Impact and Flexibility properties of the films The tensile properties of coating films were evaluated using a Universal Testing Machine from Instron, USA, in accordance with ASTM C 307. Mechanical properties, including tensile strength (with coating film thickness at 0.85 mm) and elongation at break (%), are detailed in Table 8 . The bio-based hybrid polyurethane coatings exhibit lower tensile strength but higher percent elongation when compared to AP-HEMA-PU coatings. Notably, COPU demonstrates a greater percent elongation relative to bio-based acrylic hybrid PUs. This can be attributed to the higher hydroxyl values of CO compared to bio-based hybrid polyols, which leads to increased cross-linking due to the NCO/OH ratio, resulting in a greater hard segment in COPU. Conversely, a reverse trend in percent elongation was noted for the bio-based acrylic hybrid PU. These factors indicate an increase in cross-linking between the chains, facilitating the formation of urethane linkages that enhance the strength of AP-COPU-4. Table 8 demonstrates that the COPU and bio-based acrylic hybrid PU coatings exhibit superior adhesion strength, abrasion resistance, Konig hardness, scratch resistance, impact resistance, and flexibility. The pull-off adhesion strength of the coating films applied to mild steel panels was assessed in accordance with ASTM D4541-02 utilizing the PosiTest AT-A Automatic Adhesion Tester (DeFelsko Corporation, USA). The scratch hardness of the coating films was evaluated using a Sheen automatic scratch tester-REF 705 (Komal Scientific, India). The Konig pendulum hardness of the coating films was measured with a Braive instrument (model 3034) hardness tester, following DIN 53157 standards. Additionally, the conical mandrel bend test for the coating films on mild steel tin panels was conducted according to ASTM D522. The data regarding these coating properties suggest favorable film characteristics, indicating that the overall mechanical performance of the bio-based hybrid coating is influenced by the COMA and acrylate ratio utilized in synthesizing the acrylic hybrid polyols, as well as the hard segment content, soft segment of the oil, crosslinking density, and intermolecular interactions among the hard segments. Table 8 Tensile, Adhesion, Abrasion, Hardness, Scratch, Impact and Flexibility of different 2K PU coatings. SAMPLE CODE Tensile strength (MPa) Elongation (%) Adhesion strength (MPa) Abrasion resistance (gm) Koning hardness Scrach (gm) Impact Tester Flexibility test COPU 2.7 505% 4.63 16 11.2 1600 Pass Pass AP-HEMA-PU 9.1 61% 1.4 22 8.3 1000 Fail Fail AP-COPU-1 1.4 443% 4.17 13 8.3 1700 Pass Pass AP-COPU-2 1.4 475% 5.1 12 10.3 1800 Pass Pass AP-COPU-3 1.7 481% 5.5 12 12.3 1800 Pass Pass AP-COPU-4 1.9 415% 5.6 10 13.2 2000 Pass Pass 3.8. Salt spray test of the coating hybrid films The salt spray test conducted on coated panels adhered to ASTM B117 standards, utilizing a 5% NaCl solution and an exposure duration of 600 hours. This test provides valuable insights into the corrosion resistance capabilities of the coating material when applied to mild steel panels. Observations of the salt spray test results for the coated panels were made periodically, with images documenting the 600-hour exposure period presented in Fig. 8 . The performance of the Castor and bio-based hybrid coating formulations was found to surpass that of the AP-HEMA coating film, particularly in terms of blister resistance and adhesion to the metal substrate. Notably, an increase in the percentage of COMA corresponded with improved salt spray resistance. Furthermore, the surfaces of the bio-based and COPU-based films, characterized by long-chain fatty hydrocarbon backbones, effectively create a barrier against water and corrosive agents, thereby significantly enhancing the corrosion protection offered by the bio-based polyurethane coatings. 4. Conclusions A bio-based free radical polymerizable hydroxyl functional macromonomer has been successfully synthesized and its acrylation evaluated, with a focus on its physical properties in comparison to petroleum-derived HEMA-based acrylic polyols. The resulting bio-based hybrid acrylic polyols exhibited lower viscosity than their acrylic counterparts. It was determined that these synthesized bio-based hybrid polyols are appropriate for the formulation of polyurethane (PU) materials. Consequently, the hypothesis positing that the selection of acrylates and the optimal ratio of COMA to acrylate would enhance the coating properties, as evidenced by the experimental results in comparison to HEMA-based acrylic polyols, has been supported. Although the current findings can only be regarded as preliminary, the aforementioned macromonomer demonstrates significant potential for the creation of high solid, renewable HEMA-free acrylic polyol binders suitable for two-component PU high-performance coating applications. Thus, further investigations into the efficacy of HEMA-free acrylic polyols incorporating these macromonomers could unlock extensive opportunities in the realm of bio-based acrylic polyols and their associated high-performance coatings. Declarations Declarations Competing interest The authors declare that they do not have any known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgements Author would like to thank Asian Paints staffs for their support in characterization and the authors also thank V.P. Technology and Asian Paints management for publication. References J. Yuan, D. Duanchen, Z.Z. Shou et al., Renewable thermoset polymers based on lignin and carbohydrate derived monomers. Green Chem. 20 (2018) 1131–1138. H. Yun, S. Qianqian, W. Cuina et al., Renewable epoxidized cardanol-based acrylate as a reactive diluent for UV‐curable resins, Polym. Adv. Technol. 29 (2018) 1852–1860. B. Sara, M. Eva, J. Mats Biobased UV-curable coatings based on itaconic acid, J. Coat.Tech & Res. 14 (2017) 851–861. M. Amanda, Q. Rafael, Vegetable Oils as a Chemical Platform, Poly. Gels (2018) 125–152. Z. Chaoqun, G. Thomas, M. Samy et al., Recent advances in vegetable oil-based polymers and their composites. Prog. Poly. Sci. 71 (2017) 91–143. D. Ogunniyi, Castor oil: A vital industrial raw material. Bioresour. Tech. 97 (2006) 1086–1091. K.T. Achaya, Chemical derivatives of castor oil. J. Amer.Oil Chem. Soc. 48 (1971) 758–763. H. Suhreta, J. Ivan, S.P. Zoran, Thermal and mechanical properties of glass reinforced soy- based polyurethane composites. Comp. Sci. & Tech. 65 (2005) 19–25. L. Gerard, C.R. Juan, G. Marina, et al. Novel Silicon-Containing Polyurethanes from Vegetable Oils as Renewable Resources. Synthesis and Properties. Biomacromolecules 7 (2006) 2420–2426. Z. Yuehong, K.T. Vijay, L. Yuzhan, et al., Soybean-Oil-Based Thermosetting Resins with Methacrylated Vanillyl Alcohol as Bio-Based, Low-Viscosity Comonomer. Macro. Mat. Eng. 303 (2018) 1700278. Y. Xia, R.C. Larock, Vegetable Oil-Based Polymeric Materials: Synthesis, Properties, and Applications. Green Chem. 12 (2010) 1893–1909. Z.S. Petrovic, Polyurethanes from Vegetable Oils. Polymer Reviews. 48 (2008) 109–155. A. Gandini, T.M. Lacerda, A.J.F. Carvalho, A straightforward double coupling of furan moieties onto epoxidized triglycerides: synthesis of monomers based on two renewable resources. Green Chem. 15 (2013) 1514–1519. T.M. Lacerda, A.J.F. Carvalho, A. Gandini, Two alternative approaches to the Diels–Alder polymerization of tung oil. RSC Adv. 4 (2014) 26829–26837. C. Guangxue, G. Xiaoyuan, X. Ruixin, et al., Synthesis and characterization of UV-curable castor oil-based polyfunctional polyurethane acrylate via photo-click chemistry andisocyanate polyurethane reaction. Prog. Org. Coat. 93 (2016) 11–16. B. Sara, M. Eva, J. Mats, J. Biobased UV-curable coatings based on itaconic acid. J. Coat. Tech. & Res. 14 (2017) 851–861. R. Senthilkumar, M. Vijay, Development of soy-based UV-curable acrylate oligomers and study of their film properties. Prog. Org. Coat. 76 (2013) 78–85. A.C. Fonseca, I.M. Lopes, J.F.J. Coelho, et al., Synthesis of Unsaturated Polyesters Based on Renewable Monomers: Structure/Properties Relationship and Crosslinking with 2-Hydroxyethyl Methacrylate. React. Funct. Poly. 97 (2015) 1–11. L. Ren, L. Jing, A. Sharonie, et al., High biocontent natural plant oil based UV-curable branched oligomers. Prog. Org. Coat. 105 (2017) 143–148. S. Allauddin, R. Narayan, K.V.S.N. Raju, Synthesis and Properties of Alkoxysilane Castor Oil and Their Polyurethane/Urea–Silica Hybrid Coating Films. ACS Sust. Chem. & Eng. 1 (2013) 910–918. S. Allauddin, S. Varaprasad, S. R. Thumu, et al., One-pot synthesis and physicochemical properties of high functionality soy polyols and their Polyurethane-Urea coatings. Industrial Crops & Products 85 (2016) 361–371. S.R. Ivan, B. Jaroslava, K. Ivan, et al., The properties of polyurethane hybrid materials based on castor oil. Mat.Chem. Phy. 1 (2012) 74–81. P. Tran, D. Graiver, R. Narayan, Ozone-mediated polyol synthesis from soybean oil.J. Am. Oil Chem. Soc. 82 (2005) 653–659. F. Pion, K.K. Jena, S. Allauddin, et al., Preparation and Characterization of Waterborne Hyperbranched Polyurethane-Urea and Their Hybrid Coatings. Ind. Eng. Chem. Res. 49 (2010) 4517–4527. X. Kong, G. Liu, J.M. Curtis, Novel polyurethane produced from canola oil based poly(ether ester) polyols: Synthesis, characterization and properties. Eur. Poly. J. 48 (2012) 2097–2106. I. Javni, Z.S. Petrović, A. Guo, R. Fuller, Thermal stability of polyurethanes based on vegetable oils. J. Appl. Polym. Sci. 8 (2000) 1723–1734. E. Hablot, D. Zheng, M. Bouquey, L. Avérous, Polyurethanes based on Castor Oil: Kinetics, Chemical, Mechanical and Thermal Properties, Macro. Mat. Eng. 293 (2008) 922–929. J.H. Chen, D.D. Hu, Y.D. Li, et al. Castor oil derived poly (urethane urea) networks with reprocessibility and enhanced mechanical properties. Polymer 143 (2018) 79–86. Schemes Scheme 1 is available in the Supplementary Files section Supplementary Files Scheme1.png Scheme 1. Schematic & synthetic route for Bio based Acrylic hybrid polyols and their coatings. Cite Share Download PDF Status: Published Journal Publication published 15 Feb, 2025 Read the published version in Journal of Polymer Research → Version 1 posted Reviewers agreed at journal 18 Nov, 2024 Reviewers invited by journal 29 Oct, 2024 Editor invited by journal 21 Oct, 2024 Editor assigned by journal 17 Oct, 2024 First submitted to journal 16 Oct, 2024 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-5260042","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":371530901,"identity":"feda6809-4a76-4f6f-80e5-6010ccbf9f0b","order_by":0,"name":"ALLAUDDIN SHAIK","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0001-6793-9950","institution":"Asian Paints Ltd","correspondingAuthor":true,"prefix":"","firstName":"ALLAUDDIN","middleName":"","lastName":"SHAIK","suffix":""},{"id":371530902,"identity":"a03041bc-6115-4fb7-b203-35dd7b738600","order_by":1,"name":"Kiran Kumar Nehete","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Kiran","middleName":"Kumar","lastName":"Nehete","suffix":""},{"id":371530903,"identity":"9c186407-02a3-4fa9-ac1f-7d6fad2e5c4c","order_by":2,"name":"Subarna Shyamroy","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Subarna","middleName":"","lastName":"Shyamroy","suffix":""}],"badges":[],"createdAt":"2024-10-14 09:48:58","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5260042/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5260042/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10965-025-04295-2","type":"published","date":"2025-02-15T15:57:53+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":68567953,"identity":"81937689-75aa-4444-b6aa-02e34185b75e","added_by":"auto","created_at":"2024-11-08 15:13:59","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":445430,"visible":true,"origin":"","legend":"\u003cp\u003eDigital images of the obtained bio based acrylic hybrid polyols binders clarity.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/3403011c42467b533e00d37d.png"},{"id":68567959,"identity":"72f3971e-59b7-4a81-9dd1-5ec194cad077","added_by":"auto","created_at":"2024-11-08 15:13:59","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":339308,"visible":true,"origin":"","legend":"\u003cp\u003eDigital images of the obtained bio based acrylic hybrid PU films.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/2f97ac804120f1fc2891d1bd.png"},{"id":68568482,"identity":"ed27db55-cd2d-4398-b3b8-7ec8c3fe165c","added_by":"auto","created_at":"2024-11-08 15:21:59","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":57988,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of CO, COMA, AP-HEMA and AP-CO-3.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/52d73373d251e12fd68bc796.png"},{"id":68567951,"identity":"c98e571e-97d9-4b10-8b79-b802b9494539","added_by":"auto","created_at":"2024-11-08 15:13:59","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":50904,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of COPU, AP-HEMA-PU and AP-COPU-3.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/a7f592442b904542b107037a.png"},{"id":68567952,"identity":"89e26fc7-151a-4015-ac1a-94fde146708c","added_by":"auto","created_at":"2024-11-08 15:13:59","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":93265,"visible":true,"origin":"","legend":"\u003cp\u003eE′ , tan δ versus temperature DMA curves of \u0026nbsp;different 2K PU coatings.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/30b2761462b6179f79d59aba.png"},{"id":68567958,"identity":"80881827-81e7-46c1-a9e2-d85116cd2297","added_by":"auto","created_at":"2024-11-08 15:13:59","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":65579,"visible":true,"origin":"","legend":"\u003cp\u003eE″ versus temperature DMA curves of different 2K PU coatings.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/1fadb60b6fbec6e9d2353419.png"},{"id":68567956,"identity":"ef4b1b8f-16df-4888-965a-f2f56b80f7c2","added_by":"auto","created_at":"2024-11-08 15:13:59","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":78599,"visible":true,"origin":"","legend":"\u003cp\u003eTGA curves of \u0026nbsp;\u0026nbsp;different 2K PU coatings.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/3967799aca157cc76456f812.png"},{"id":68569478,"identity":"dc64cf76-cfab-42bc-a07c-f673871dd72a","added_by":"auto","created_at":"2024-11-08 15:29:59","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":436750,"visible":true,"origin":"","legend":"\u003cp\u003eSalt spray images of different 2K PU coatings.\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/be465815846964f40da8f918.png"},{"id":76487606,"identity":"2761a1f7-730d-4d1a-8298-d1fce44574bc","added_by":"auto","created_at":"2025-02-17 16:09:50","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3076587,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/a26d6c7a-36c2-450b-9519-e16e78c890d7.pdf"},{"id":68567950,"identity":"66ddd7d5-c97e-424a-ba46-8c634ba439ac","added_by":"auto","created_at":"2024-11-08 15:13:59","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":54120,"visible":true,"origin":"","legend":"\u003cp\u003eScheme 1. Schematic \u0026amp; synthetic route for Bio based Acrylic hybrid polyols and their coatings.\u003c/p\u003e","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-5260042/v1/35a56e04c5f09d1e11006c42.png"}],"financialInterests":"","formattedTitle":"Effective Studies of bio-derived free radical polymerizable hydroxyl functional Macromonomer for replacement of Hydroxyl Ethyl Methacrylate (HEMA) in acrylic polyols and their Polyurethane-Urea Coatings","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eRecent trends in industry and literature have highlighted the growing necessity for awareness regarding sustainable development platforms. This shift aims to foster the creation of environmentally friendly functional macromers and polymers, as well as to substitute petroleum-based components and polymer materials with those derived from renewable resources.\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e In particular, the use of agricultural feedstocks, such as plant oils, is gaining traction as a sustainable approach to developing environmentally friendly materials and polymers. This shift aims to replace existing petroleum-based monomers and polymers, focusing on both cost-effectiveness and performance attributes. \u003csup\u003e\u003cspan additionalcitationids=\"CR4\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e Plant oils are vital components in the synthesis of bio-based polymers that demonstrate superior performance. Among these oils, castor oil is particularly advantageous as a bio-based polyol, given its natural hydroxyl functionalities. This characteristic allows for its direct incorporation into polyurethane production, resulting in improved gloss, flexibility, and water resistance.\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e The synthesized polyurethane materials derived from plant oils exhibit limited mechanical strength, stiffness, and thermal stability. These characteristics are essential for high-performance structural applications. \u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e However, the inherent chemical structure of plant oils contains non-conjugated carbon\u0026ndash;carbon double bonds, which lack the reactivity necessary to promote free radical polymerization effectively.\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e Hence, the functionalization of plant oils is vital for their use as core building blocks in bio-based polymers. It is a well-established reality that a plant oil feedstock is being created for blending or structural modifications in a range of coating applications. \u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e The unsaturation present in plant oils exhibits low reactivity in terms of polymerization and chemical modification, necessitating elevated temperature conditions. \u003csup\u003e\u003cspan additionalcitationids=\"CR14\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e As a significant renewable resource, natural plant oils have been utilized to develop bio-based UV curable materials through a variety of chemical methods. \u003csup\u003e\u003cspan additionalcitationids=\"CR17 CR18\" citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e The incorporation of functional reactive sites within plant oils, as well as the presence of renewable constituents with appropriate active unsaturation functionalities for polymerization, remains an encouraging development. However, there is a need for further progress in utilizing these modified plant oils in acrylic polymerization. The present research is designed to showcase the feasibility of a bio-derived free radical polymerizable hydroxyl functional macro-monomer in the conventional acrylation process. It also aims to compare the physical and coating properties of the resulting polyurethanes (PUs) with those of acrylic polyols (AP-HEMA) produced from the same conventional acrylate monomers, including Methyl methacrylate (MMA) and Butyl acrylate (BA), along with a commercially available petroleum-derived acrylate hydroxyl functionality, HEMA. Thus, the focus of this research is on evaluating the effectiveness of replacing HEMA in the conventional acrylation process with a free radical polymerizable hydroxyl functional macromonomer (COMA) obtained from castor oil.\u003c/p\u003e"},{"header":"2. Experimental section","content":"\u003cp\u003e \u003cb\u003e2.1. Materials.\u003c/b\u003e Castor oil (CO) was sourced from the commercial market, exhibiting characteristic properties with a hydroxyl value ranging from 162 to 165 mg KOH/g and an acid value below 2 mg KOH/g. Isophorone diisocyanate (IPDI) was acquired from Evonik Industries in Germany. All acrylic monomers, including methyl methacrylate (MMA), butyl acrylate (BA), and hydroxyl ethyl methacrylate (HEMA), were obtained from various commercial suppliers. The initiator, Di-tert-butyl peroxide (DTBP), was procured from Luperox and is of analytical grade. Maleic anhydride (MA), dibutyltin dilaurate (DBTDL), and other chemicals were also of analytical grade and utilized without additional purification.\u003c/p\u003e \u003cp\u003e \u003cb\u003e2.2. Synthesis of bio derived free radical polymerizable hydroxyl functionality macro monomer (COMA).\u003c/b\u003e The Adduct (COMA) was synthesized from 100 grams of castor oil and 4 grams of maleic anhydride utilizing a four-neck round-bottom flask fitted with a mechanical stirrer, nitrogen purge, and thermometer, with the reaction conducted at a temperature of 90\u0026deg;C. The progress of the anhydride ring-opening reaction involving maleic anhydride and castor oil was tracked using an FT-IR spectrophotometer, observing the disappearance of the anhydride peak at 1850 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in the final spectra. The modified castor oil, which possesses free radical polymerizable hydroxyl functionality, is referred to as COMA throughout this manuscript. The schematic representation of COMA is illustrated in Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e \u003cb\u003e2.3. Synthesis of Acrylic Polyol using HEMA (AP-HEMA).\u003c/b\u003e \u003c/p\u003e \u003cp\u003eAP-HEMA was synthesized via the solution polymerization of acrylate monomers in butyl acetate solvent. The butyl acetate was placed in a four-necked flask equipped with a thermometer, condenser, and motor-driven stirrer. Separately, a mixture of the monomers MMA, BA, and HEMA, along with 1.4 g of the initiator DTBP, was prepared in a round-bottom flask. The monomer mixture was introduced into the system using a peristaltic pump over a duration of three hours at a temperature of 120\u0026deg;C. An additional 0.2 g of DTBP was then added, and the polymerization process continued for an additional hour at the same temperature to ensure complete conversion. The resulting acrylic polyol was designated as AP-HEMA, with a hydroxyl value of 93.64 mg KOH/g.\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Synthesis of Bio based Acrylic Hybrid Polyols using COMA.\u003c/h2\u003e \u003cp\u003eFour experimental bio-based acrylic hybrid polyols were synthesized utilizing varying weight ratios of COMA while maintaining constant weight ratios of acrylate in the acrylation process. The weight amounts of the different raw materials employed in the reaction are presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. A similar procedure was followed for the acrylation of COMA. Butyl acetate solvent was utilized in a four-necked flask equipped with a thermometer, condenser, and motor-driven stirrer. A separate mixture of the monomers MMA, BA, and COMA, along with 1.4 g of the initiator DTBP, was prepared in a round-bottom flask. The monomer mixture was introduced into the system via a peristaltic pump over a duration of three hours at a temperature of 120\u0026deg;C. An additional 0.2 g of DTBP was incorporated into the system, and the polymerization reaction was allowed to proceed for an additional hour at the same temperature to ensure complete conversion. The acrylic polyols derived from COMA are designated as AP-CO-1, AP-CO-2, AP-CO-3, and AP-CO-4. Notably, only AP-CO-3 exhibits a hydroxyl value that is comparable to that of AP-HEMA. Digital images of the resulting bio-based acrylic hybrid polyol binders are illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The bio content, specifically the castor oil content, in each formulation was calculated based on 100 parts by weight of the total formulation, as detailed in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, with a solid content of 50% maintained across all binder formulations. The properties of the synthesized polyols are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, while Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e provides a schematic representation of the structure and process of the bio-based acrylic hybrid polyol.\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\u003eVarious weight ratios (in grams) used to prepare the bio based acrylic hybrid polyols.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"8\"\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 \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample code\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMA\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCO\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eMMA\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eBA\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eHEMA\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eCOMA\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eCO:Acrylate\u003c/p\u003e \u003cp\u003e( %)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCOMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAPCO-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e37:63\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAPCO-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e49\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e54:46\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAPCO-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e79\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e66:34\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAPCO-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e158\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e80:20\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\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\u003eMole ratios used to prepare the different 2K PU coatings.\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=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample code\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eIPDI(OH:NCO)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCOPU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1:1.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA-PU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1:1.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1:1.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1:1.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1:1.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1:1.6\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=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.5. Synthesis of Polyurethane-Urea coating films.\u003c/h2\u003e \u003cp\u003eThe synthesized polyols were subsequently reacted with IPDI at an NCO:OH ratio of 1.6:1 at approximately 80\u0026deg;C to produce \u0026ndash;NCO terminated polyurethane pre-polymers. These pre-polymers were then applied onto releasing paper using a manually operated square film applicator to achieve uniform final coating films. The \u0026ndash;NCO terminated pre-polymer was exposed to atmospheric moisture and laboratory humidity for a duration of 15 days to facilitate moisture curing. The complete curing of the films was indicated by the disappearance of the \u0026ndash;NCO peak at 2270 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in the FT-IR spectroscopy analysis. The polyurethanes derived from AP-CO-1, AP-CO-2, AP-CO-3, and AP-CO-4 were designated as AP-COPU-1, AP-COPU-2, AP-COPU-3, and AP-COPU-4, respectively, while the polyurethane from AP-HEMA was labeled as AP-HEMA-PU. For reference and comparison, a castor oil-based polyurethane was synthesized using solely castor oil (CO) and was designated as COPU. The compositions of the various polyurethanes are detailed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Digital images of the resulting bio-based polyurethane films, which have a thickness of 150 \u0026micro;m, are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\n\u003ch3\u003e3. 1. Effect of structural variation on molecular weight, viscosity, and glass transition temperature\u003c/h3\u003e\n\u003cp\u003eThe characterization of acrylic polyols, CO, and their pre-polymers was conducted utilizing gel permeation chromatography on a Varian ProStar chromatograph model-210 from the USA. A sample concentration of 0.1 g per 10 mL was prepared by dissolving the samples in THF, and the experiments were performed at a flow rate of 1.0 mL/min with THF serving as the mobile phase. Calibration of the columns was achieved using Aldrich polystyrene standards. The polymerization of the COMA backbone with MMA and BA significantly influenced the molecular weight, viscosity, and glass transition temperature in comparison to unmodified castor oil. Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e illustrates the schematic steps involved in the synthesis of bio-based acrylic hybrid polyols and their corresponding polyurethanes, while Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e presents the physical characteristics of the pre-polymers and various monomer reactants utilized in the synthesis of the bio-based acrylic hybrid polyols, along with their respective weight ratios. The analysis of molecular weights (Mw) was conducted through the GPC technique utilizing tetrahydrofuran as the solvent, with the findings presented in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The variation in weight ratios of COMA has resulted in an increase in molecular weight, which can be attributed to the development of an acrylic network. Upon reviewing the GPC data, it is evident that the Mw and Mn of bio-based hybrid polyols are superior to those of CO and COMA. This enhancement is a result of the polymerization involving MMA and BA with the bio-derived free radical polymerizable hydroxyl functionality macromonomer (COMA), which is considerably less reactive than the petroleum-derived HEMA. As a result, the molecular weight of AP-HEMA is greater than that of the bio-based acrylic hybrid polyols. Additionally, the viscosities of the bio-based hybrid polyols, measured at 50% solid content and 27.4\u0026deg;C using the ICI cone and plate viscometer VR-4410 at 900 RPM, were observed to be higher than those of COMA and CO. This increase in viscosity is expected due to the radical polymerization process, as shown in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The dominance of higher molecular weight polymers leads to increased viscosity, which can be attributed to the polymerization process occurring in AP-HEMA. The glass transition temperature characteristics of CO, COMA, and their acrylic polyols, along with AP-HEMA, were examined using Differential Scanning Calorimetry (DSC) on a TAQ 2000 (TA Instruments, USA). The samples were subjected to heating from \u0026minus;\u0026thinsp;70 to 150\u0026deg;C at a rate of 10\u0026deg;C/min in a nitrogen atmosphere with a flow rate of 30 mL/min, and the data is presented in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. This finding further substantiates that the acrylic grafting of COMA with MMA and BA acrylates occurred through radical polymerization, resulting in an increase in the Tg of the binders.\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\u003eCharacteristics of different binders.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"8\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" 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=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample ID\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMn (gm/mol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMw (gm/mol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eMz (gm/mol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eP.D.I\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eOH value\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eViscosity (cps)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eTg\u003csup\u003e0\u003c/sup\u003eC\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1227\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1384\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1471\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1.12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e165.48\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e640\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e-30.68\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCOMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1359\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1539\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1676\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e136.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e890\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e-28.8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e12305\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e47603\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e114840\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e3.86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e93.64\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e6000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e8.4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3493\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e17808\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e59246\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e3.09\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e73.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e2300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e1.8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2192\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e7889\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e28939\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e3.59\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e82.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e1.4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1982\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e6273\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e22192\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e3.16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e90.85\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e900\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e0.9\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1837\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3732\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e8859\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e105.21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e0.4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.2. FTIR analysis of the hybrid polyols and their PU-Urea films\u003c/h2\u003e \u003cp\u003eThe chemical structures of acrylic polyols, oils, and their hybrid polyols, along with their polyurethane films, were analyzed using Fourier transform infrared spectroscopy (FTIR) on a PerkinElmer Spectrum One instrument. The structural characteristics of both modified and unmodified castor oil were examined through FTIR. The FT-IR spectra for castor oil, COMA, and its acrylic hybrid, as well as AP-HEAM polyol, are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. In the case of castor oil, a broad peak at 3454 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponds to the absorption of the -OH functional group, while the stretching frequency of the -HC\u0026thinsp;=\u0026thinsp;CH- double bond is observed at 1640 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Notably, no peaks associated with the cyclic anhydride group at 1779 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1849 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were detected in COMA, suggesting that the anhydride ring was consumed during the reaction with castor oil. Consequently, the newly formed unsaturation in the COMA spectra is indicated by the absorption peak at 1640 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,\u003csup\u003e[20]\u003c/sup\u003e which can be attributed to the stretching frequency of the\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e\u0026ndash;HC\u0026thinsp;=\u0026thinsp;CH\u0026ndash; double bond. When castor oil reacts with MA, a significant reduction in the -OH peak is observed, while the peak corresponding to the double bond is notably enhanced. The peaks observed at 1385 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and within the range of 2800\u0026ndash;3000 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are attributed to the bending of \u0026ndash;C\u0026ndash;H bonds from the terminal methyl group and the aliphatic \u0026ndash;C\u0026ndash;H bonds, respectively. This suggests that the integration of acid functionality into the castor oil backbone was effectively achieved through the ring-opening reaction of the anhydride with the secondary hydroxyl group present in castor oil. The corresponding acrylic grafting of COMA and AP-HEMA is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. In this figure, AP-HEMA displays an \u0026ndash;OH stretching at 3532 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (broad band), \u0026gt;C\u0026thinsp;=\u0026thinsp;O stretching (acrylic ester) at 1732 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, \u0026ndash;CH\u003csub\u003e2\u003c/sub\u003e stretching at 2957 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, \u0026ndash;C\u0026ndash;H bending at 1452 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1387 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, as well as C\u0026ndash;O stretching (acrylic) at 1072 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1167 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The incorporation of COMA into MMA and BA resulted in the disappearance of the intensity peak around 1697 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, indicating that the unsaturation of MA underwent polymerization with acrylates.\u003c/p\u003e \u003cp\u003eThe FT-IR spectra of the polyurethane coating films are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e and exhibit notable similarities. Characteristic absorption bands include the \u0026ndash;N\u0026ndash;H stretching observed between 3500\u0026thinsp;\u0026minus;\u0026thinsp;3300 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, the urethane carbonyl associated with ─NH\u0026ndash;CO\u0026ndash;O (alongside secondary amide peaks) and ─CO─O (ester carbonyl) within the range of 1740\u0026thinsp;\u0026minus;\u0026thinsp;1728 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, as well as a combination of ─C\u0026ndash;N and ─N\u0026ndash;H out-of-plane bending stretching at 1525 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which are evident across all spectra. The absorbance features in the spectra of the polyurethane coating films, derived from bio-based acrylic hybrid polyols, indicate the presence of castor oil-derived polymeric films, characterized by the stretching vibrations of the aliphatic ─CH\u003csub\u003e2\u003c/sub\u003e groups at 2925 and 2855 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and the \u0026ndash;CH\u003csub\u003e2\u003c/sub\u003e bending vibrations at 1385 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e [21].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.3. DMA analysis of the hybrid films\u003c/h2\u003e \u003cp\u003eThermal analysis was conducted using a dynamic mechanical analysis (DMA) TAQ800 instrument from TA Instruments, USA, operating in tensile mode at a frequency of 1 Hz and a heating rate of 3\u0026deg;C/min. The films were scanned over a temperature range from \u0026minus;\u0026thinsp;60 to 150\u0026deg;C. The viscoelastic properties of the coating films were examined with the DMA equipment, yielding results for the tensile storage modulus (E\u0026prime;), the corresponding loss modulus (E\u0026Prime;), and the loss factor tan δ, which is defined as the ratio of the loss modulus to the storage modulus, E\u0026Prime;/E\u0026prime;. The glass transition temperature (Tg) values of the PU-urea films were determined from the peaks observed in the tan δ curves. Additionally, the crosslink density (υe) of the films was calculated using the formula provided below.\u003c/p\u003e \u003cp\u003eυe\u0026thinsp;=\u0026thinsp;E\u0026prime; / 3RT\u003c/p\u003e \u003cp\u003eWhere R is the universal gas constant, and T the temperature in K. E\u0026prime; values in the rubbery region at T\u0026thinsp;\u0026gt;\u0026thinsp;Tg were taken to calculate υe by using above formula.\u003c/p\u003e \u003cp\u003eFigures \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e illustrate the relationship between E\u0026prime;, E\u0026Prime;, and tan δ as a function of temperature (T), with the dynamic properties of the films represented in the accompanying curves. The data is consolidated in Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The DMA curves of the films exhibit characteristics akin to homogeneous polymeric networks concerning the storage modulus (E\u0026prime;) curves. Notably, AP-HEMA-PU demonstrates superior E\u0026prime; and Tg values when compared to COPU and other bio-based acrylic hybrid PUs; however, the crosslink density of the coating films is influenced by the hydroxyl values of the resins. The Tg values for COPU, AP-HEMAPU, AP-COPU-1, AP-COPU-2, AP-COPU-3, and AP-COPU-4 are recorded as 27.21, 79, 29.7, 28, 26, and 21.4\u0026deg;C, respectively. At 20\u0026deg;C, the E\u0026prime; values for COPU, AP-HEMAPU, AP-COPU-1, AP-COPU-2, AP-COPU-3, and AP-COPU-4 hybrid coating films are 6.4 x 10\u003csup\u003e7\u003c/sup\u003e, 1.24 x 10\u003csup\u003e9\u003c/sup\u003e, 3.08 x 10\u003csup\u003e7\u003c/sup\u003e, 2.41 x 10\u003csup\u003e7\u003c/sup\u003e, and 2.52 x 10\u003csup\u003e7\u003c/sup\u003e Pa, respectively. In the rubbery region at Tg\u0026thinsp;+\u0026thinsp;5\u0026deg;C and Tg\u0026thinsp;+\u0026thinsp;30\u0026deg;C, an increase in OH functionality due to a higher percentage of oil incorporation results in AP-COPU-4 exhibiting a greater storage modulus, followed by AP-COPU-3, AP-COPU-2, and AP-COPU-1. This is attributed to the higher hydroxyl functionality leading to increased crosslink density compared to other bio-based acrylic hybrid PUs, which may enhance the mechanical properties of AP-COPU-4. Furthermore, based on the DMA Tg data, it is possible to enhance the Tg of bio-based acrylic hybrid PUs by selecting monomers according to their Tg and the ratio of COMA to acrylate, achieving results comparable to conventional petroleum-derived HEMA-based acrylic polyols. \u003csup\u003e[22\u0026ndash;23]\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \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\u003eDMA data of the different 2K PU coatings.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" 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=\"left\" 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=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample ID\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTg(\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTan δmax\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eE\u0026prime; at 20\u0026deg;C [Pa]\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eE\u0026prime; at Tg\u0026thinsp;+\u0026thinsp;5\u0026deg;C\u003c/p\u003e \u003cp\u003e[Pa]\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eE\u0026prime; at\u003c/p\u003e \u003cp\u003eTg\u0026thinsp;+\u0026thinsp;30\u0026deg;C\u003c/p\u003e \u003cp\u003e[Pa]\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003cem\u003eυ\u003c/em\u003e\u003csub\u003ee\u003c/sub\u003e (Tg\u0026thinsp;+\u0026thinsp;5\u0026deg;C)\u003c/p\u003e \u003cp\u003e(mole/cm\u003csup\u003e3\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCOPU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e27.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.78\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e6.4 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.8 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.7 x 10\u003csup\u003e6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.36 x 10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA-PU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e79.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.64\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.24 x 10\u003csup\u003e9\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.04 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.8 x 10\u003csup\u003e6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.16 x 10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e29.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.33\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3.08 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.8 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.2 x 10\u003csup\u003e6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.04 x 10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e28.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.41 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.6 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.1 x 10\u003csup\u003e6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.78 x 10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e26.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.98\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3.15 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.52 x 10\u003csup\u003e6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.31 x 10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e21.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.99\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.52 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.3 x 10\u003csup\u003e7\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.41 x 10\u003csup\u003e6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.74 x 10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\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=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.4. Contact angle of the hybrid films\u003c/h2\u003e \u003cp\u003eThe contact angle was assessed using the DSA 100 (KRUSS) instrument via the sessile drop method. Measurements of the contact angle (CA) were conducted on the films with water and ethylene glycol serving as probe liquids. The resulting surface free energies (SFE) and contact angle data are compiled in Table\u0026nbsp;\u003cspan refid=\"Tab5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. The COPU and bio-based acrylic hybrid polyols exhibit superior hydrophobic characteristics compared to the AP-HEMA-PU coatings. Specifically, the AP-HEMA-PU demonstrates a lower water CA of approximately 68.5\u0026deg;, while the bio-based acrylic hybrid PU surfaces show water CAs ranging from 75.4\u0026deg; to 80.5\u0026deg;, and the COPU presents a water CA of about 81.9\u0026deg;. The enhancement in water contact angle for the bio-based hybrid PU can be attributed to the grafting of COMA in the acrylate monomers, which improves the hydrophobic properties of the bio-based hybrid coating by increasing the weight ratio of COMA during acrylation, leading to the formation of fatty acid chains through the incorporation process. Similar oleophobic properties were observed with ethylene glycol.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab5\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 5\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eContact angle data of the different 2K PU coatings.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" 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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSample code\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003eContact angle (Ɵ)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSFE (mN/m)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eEthylene glycol\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e68.56\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e57.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e52.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e75.47\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e59.10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e47.7\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e76.48\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e61.85\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e44.7\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e78.53\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e63.40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e42.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-CO-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e80.52\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e66.78\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e41.8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCO-PU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e81.94\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e68.54\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e40.1\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\u003e3.5. Swelling properties of the films\u003c/h2\u003e \u003cp\u003eTable\u0026nbsp;\u003cspan refid=\"Tab6\" class=\"InternalRef\"\u003e6\u003c/span\u003e also shows the water and toluene swelling as a function of immersion time (72 hr) of the films. The swelling ratio (Q %) in water is calculated using following equation \u003csup\u003e[22]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab6\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 6\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSwelling properties of different 2K PU coatings.\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=\"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=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFilm samples\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eQ %\u003c/p\u003e \u003cp\u003e(water)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eQ\u003csub\u003eL\u003c/sub\u003e%\u003c/p\u003e \u003cp\u003e(water)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eW\u003csub\u003et\u003c/sub\u003e%\u003c/p\u003e \u003cp\u003e(Toluene)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eW\u003csub\u003eL\u003c/sub\u003e%\u003c/p\u003e \u003cp\u003e(Toluene)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCO-PU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.65\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e136.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e3.2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA-PU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.87\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e60.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e12.1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e253.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e28.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.85\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e236.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e24.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-3\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\u003e1.34\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e214.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e17.2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e167.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e10.8\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\u003eSwelling ratio (Q), % = [(W\u003csub\u003es\u003c/sub\u003e \u0026minus; W\u003csub\u003ed\u003c/sub\u003e)/W\u003csub\u003ed\u003c/sub\u003e] \u0026times; 100\u003c/p\u003e \u003cp\u003eAmounts of the films dissolved into the water: (Q\u003csub\u003eL\u003c/sub\u003e) % = [(W\u003csub\u003ed\u003c/sub\u003e-W\u003csub\u003eod\u003c/sub\u003e)/W\u003csub\u003ed\u003c/sub\u003e] x 100\u003c/p\u003e \u003cp\u003eWhere W\u003csub\u003ed\u003c/sub\u003e is the weight of the dry sample as such and W\u003csub\u003es\u003c/sub\u003e is the weight of the swollen sample. W\u003csub\u003eod\u003c/sub\u003e is the weight of oven dried sample.\u003c/p\u003e \u003cp\u003eIn toluene, calculation was done according to the following equations.\u003c/p\u003e \u003cp\u003eW\u003csub\u003et\u003c/sub\u003e (%) = [(W\u003csub\u003e1\u003c/sub\u003e \u0026ndash; W\u003csub\u003e0\u003c/sub\u003e)/W\u003csub\u003e2\u003c/sub\u003e] \u0026times; 100\u003c/p\u003e \u003cp\u003eW\u003csub\u003et\u003c/sub\u003e: amounts of toluene absorption by the film.\u003c/p\u003e \u003cp\u003eW\u003csub\u003eL\u003c/sub\u003e (%) = [(W\u003csub\u003e0\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;W\u003csub\u003e2\u003c/sub\u003e)/W\u003csub\u003e0\u003c/sub\u003e] \u0026times; 100\u003c/p\u003e \u003cp\u003eW\u003csub\u003eL\u003c/sub\u003e: amounts of the films dissolved into the toluene solution.\u003c/p\u003e \u003cp\u003eWhere known weight (W\u003csub\u003e0\u003c/sub\u003e) of the films, the towel down dry sample weight (W\u003csub\u003e1\u003c/sub\u003e) and the oven-dried sample weight (W\u003csub\u003e2\u003c/sub\u003e) were obtained.\u003c/p\u003e \u003cp\u003eAll films demonstrated considerable swelling in toluene solvent, as illustrated in Table\u0026nbsp;\u003cspan refid=\"Tab6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. The data from the overall swelling studies indicate that the bio-based hybrid polyurethane coating films exhibit lower solvent resistance but higher water resistance when compared to AP-HEMA-PU coatings. The inclusion of COMA generally reduced the degree of swelling, suggesting that the addition of fatty hydrocarbon chain networks within the castor oil backbone may be responsible for this effect. This phenomenon can be attributed to the expected characteristics of the network model, as well as the asymmetrical chemical structures present in the bio-based hybrid acrylic polyurethane films [24].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.6. TGA analysis of the hybrid films\u003c/h2\u003e \u003cp\u003eThermogravimetric analysis was performed using a Mettler Toledo TGA 1/SDTAe apparatus, with a heating rate set at 10\u0026deg;C per minute in a nitrogen atmosphere. The thermal degradation profiles of PU-Urea films are illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. The volatilization of residual solvents and trapped moisture within the coating films occurs during decomposition at temperatures ranging from 100 to 150\u0026deg;C. Studies on oil-based PU-urea coating films reveal three distinct decomposition stages. \u003csup\u003e[ 25\u0026ndash;26]\u003c/sup\u003e In the initial stage, PU exhibits a gradual decomposition up to 335\u0026deg;C, resulting in a weight loss of 30\u0026ndash;43%. The TGA curves for COPU and bio-based acrylic hybrid PU indicate that the primary degradation process occurs between 350\u0026deg;C and 365\u0026deg;C, while AP-HEMA-PU shows degradation at temperatures between 370\u0026deg;C and 420\u0026deg;C. A summary of the comparative TGA data, including Ton (initial decomposition temperature), Tend (final decomposition temperature), Tmax (maximum decomposition temperature), and percentage weight remaining at 250\u0026deg;C, 350\u0026deg;C, and 450\u0026deg;C, is presented in Table\u0026nbsp;\u003cspan refid=\"Tab7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. The data indicate that the thermal stability of the PU coating films improves with increased oil content, suggesting that higher unsaturation levels necessitate additional thermal energy to break down the extra bonds prior to complete network degradation. \u003csup\u003e[ 27\u0026ndash;28]\u003c/sup\u003e This behavior may be influenced by the network structure and various chemical structural factors, including steric strain and the conformational arrangements of the groups. The TGA curves and corresponding data suggest that the thermal stability of the bio-based acrylic hybrid films surpasses that of the AP-HEMA-PU.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab7\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 7\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eTGA data of different 2K PU coatings.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"9\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" 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=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSample ID\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eT\u003csub\u003eon\u003c/sub\u003e (\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c5\" namest=\"c3\"\u003e \u003cp\u003eT\u003csub\u003emax\u003c/sub\u003e (\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eT\u003csub\u003eend\u003c/sub\u003e(\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c9\" namest=\"c7\"\u003e \u003cp\u003e%weight remaining at\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eT\u003csub\u003emax 1\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eT\u003csub\u003emax 2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eT\u003csub\u003emax 3\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003e250 \u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003e350 \u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003e450 \u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCOPU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e242\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e320\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e356\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e410\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e469\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e99.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e56.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e4.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA-PU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e256\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e370\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e415\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e453\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e93.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e73.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e1.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e250\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e305\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e325\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e403\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e466\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e97.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e76.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e4.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e248\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e307\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e325.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e406\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e469\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e96.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e71.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e7.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e246\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e326\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e365\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e405\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e469\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e97.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e69.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e7.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e232\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e318\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e362\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e411\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e472\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e96.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e68.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e10.4\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=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.7. Tensile, Adhesion, Abrasion, Hardness, Scratch, Impact and Flexibility properties of the films\u003c/h2\u003e \u003cp\u003eThe tensile properties of coating films were evaluated using a Universal Testing Machine from Instron, USA, in accordance with ASTM C 307. Mechanical properties, including tensile strength (with coating film thickness at 0.85 mm) and elongation at break (%), are detailed in Table\u0026nbsp;\u003cspan refid=\"Tab8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. The bio-based hybrid polyurethane coatings exhibit lower tensile strength but higher percent elongation when compared to AP-HEMA-PU coatings. Notably, COPU demonstrates a greater percent elongation relative to bio-based acrylic hybrid PUs. This can be attributed to the higher hydroxyl values of CO compared to bio-based hybrid polyols, which leads to increased cross-linking due to the NCO/OH ratio, resulting in a greater hard segment in COPU. Conversely, a reverse trend in percent elongation was noted for the bio-based acrylic hybrid PU. These factors indicate an increase in cross-linking between the chains, facilitating the formation of urethane linkages that enhance the strength of AP-COPU-4. Table\u0026nbsp;\u003cspan refid=\"Tab8\" class=\"InternalRef\"\u003e8\u003c/span\u003e demonstrates that the COPU and bio-based acrylic hybrid PU coatings exhibit superior adhesion strength, abrasion resistance, Konig hardness, scratch resistance, impact resistance, and flexibility. The pull-off adhesion strength of the coating films applied to mild steel panels was assessed in accordance with ASTM D4541-02 utilizing the PosiTest AT-A Automatic Adhesion Tester (DeFelsko Corporation, USA). The scratch hardness of the coating films was evaluated using a Sheen automatic scratch tester-REF 705 (Komal Scientific, India). The Konig pendulum hardness of the coating films was measured with a Braive instrument (model 3034) hardness tester, following DIN 53157 standards. Additionally, the conical mandrel bend test for the coating films on mild steel tin panels was conducted according to ASTM D522. The data regarding these coating properties suggest favorable film characteristics, indicating that the overall mechanical performance of the bio-based hybrid coating is influenced by the COMA and acrylate ratio utilized in synthesizing the acrylic hybrid polyols, as well as the hard segment content, soft segment of the oil, crosslinking density, and intermolecular interactions among the hard segments.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab8\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 8\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eTensile, Adhesion, Abrasion, Hardness, Scratch, Impact and Flexibility of different 2K PU coatings.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"9\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" 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=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSAMPLE CODE\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTensile strength (MPa)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eElongation (%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eAdhesion strength (MPa)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eAbrasion resistance (gm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eKoning hardness\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eScrach (gm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eImpact Tester\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003eFlexibility test\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCOPU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e505%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.63\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e11.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1600\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-HEMA-PU\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e9.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e61%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e8.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003eFail\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003eFail\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e443%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e8.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1700\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e475%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e10.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e481%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e12.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAP-COPU-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e415%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e13.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e2000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003ePass\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003ePass\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=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.8. Salt spray test of the coating hybrid films\u003c/h2\u003e \u003cp\u003eThe salt spray test conducted on coated panels adhered to ASTM B117 standards, utilizing a 5% NaCl solution and an exposure duration of 600 hours. This test provides valuable insights into the corrosion resistance capabilities of the coating material when applied to mild steel panels. Observations of the salt spray test results for the coated panels were made periodically, with images documenting the 600-hour exposure period presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. The performance of the Castor and bio-based hybrid coating formulations was found to surpass that of the AP-HEMA coating film, particularly in terms of blister resistance and adhesion to the metal substrate. Notably, an increase in the percentage of COMA corresponded with improved salt spray resistance. Furthermore, the surfaces of the bio-based and COPU-based films, characterized by long-chain fatty hydrocarbon backbones, effectively create a barrier against water and corrosive agents, thereby significantly enhancing the corrosion protection offered by the bio-based polyurethane coatings.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eA bio-based free radical polymerizable hydroxyl functional macromonomer has been successfully synthesized and its acrylation evaluated, with a focus on its physical properties in comparison to petroleum-derived HEMA-based acrylic polyols. The resulting bio-based hybrid acrylic polyols exhibited lower viscosity than their acrylic counterparts. It was determined that these synthesized bio-based hybrid polyols are appropriate for the formulation of polyurethane (PU) materials. Consequently, the hypothesis positing that the selection of acrylates and the optimal ratio of COMA to acrylate would enhance the coating properties, as evidenced by the experimental results in comparison to HEMA-based acrylic polyols, has been supported. Although the current findings can only be regarded as preliminary, the aforementioned macromonomer demonstrates significant potential for the creation of high solid, renewable HEMA-free acrylic polyol binders suitable for two-component PU high-performance coating applications. Thus, further investigations into the efficacy of HEMA-free acrylic polyols incorporating these macromonomers could unlock extensive opportunities in the realm of bio-based acrylic polyols and their associated high-performance coatings.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eDeclarations Competing interest\u003c/h2\u003e \u003cp\u003eThe authors declare that they do not have any known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eAuthor would like to thank Asian Paints staffs for their support in characterization and the authors also thank V.P. Technology and Asian Paints management for publication.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eJ. Yuan, D. Duanchen, Z.Z. Shou et al., Renewable thermoset polymers based on lignin and carbohydrate derived monomers. Green Chem. 20 (2018) 1131\u0026ndash;1138.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Yun, S. Qianqian, W. Cuina et al., Renewable epoxidized cardanol-based acrylate as a reactive diluent for UV‐curable resins, Polym. Adv. Technol. 29 (2018) 1852\u0026ndash;1860.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eB. Sara, M. Eva, J. Mats Biobased UV-curable coatings based on itaconic acid, J. Coat.Tech \u0026amp; Res. 14 (2017) 851\u0026ndash;861.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eM. Amanda, Q. Rafael, Vegetable Oils as a Chemical Platform, Poly. Gels (2018) 125\u0026ndash;152.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ. Chaoqun, G. Thomas, M. Samy et al., Recent advances in vegetable oil-based polymers and their composites. Prog. Poly. Sci. 71 (2017) 91\u0026ndash;143.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eD. Ogunniyi, Castor oil: A vital industrial raw material. Bioresour. Tech. 97 (2006) 1086\u0026ndash;1091.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK.T. Achaya, Chemical derivatives of castor oil. J. Amer.Oil Chem. Soc. 48 (1971) 758\u0026ndash;763.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Suhreta, J. Ivan, S.P. Zoran, Thermal and mechanical properties of glass reinforced soy- based polyurethane composites. Comp. Sci. \u0026amp; Tech. 65 (2005) 19\u0026ndash;25.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eL. Gerard, C.R. Juan, G. Marina, et al. Novel Silicon-Containing Polyurethanes from Vegetable Oils as Renewable Resources. Synthesis and Properties. Biomacromolecules 7 (2006) 2420\u0026ndash;2426.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ. Yuehong, K.T. Vijay, L. Yuzhan, et al., Soybean-Oil-Based Thermosetting Resins with Methacrylated Vanillyl Alcohol as Bio-Based, Low-Viscosity Comonomer. Macro. Mat. Eng. 303 (2018) 1700278.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY. Xia, R.C. Larock, Vegetable Oil-Based Polymeric Materials: Synthesis, Properties, and Applications. Green Chem. 12 (2010) 1893\u0026ndash;1909.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZ.S. Petrovic, Polyurethanes from Vegetable Oils. Polymer Reviews. 48 (2008) 109\u0026ndash;155.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Gandini, T.M. Lacerda, A.J.F. Carvalho, A straightforward double coupling of furan moieties onto epoxidized triglycerides: synthesis of monomers based on two renewable resources. Green Chem. 15 (2013) 1514\u0026ndash;1519.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eT.M. Lacerda, A.J.F. Carvalho, A. Gandini, Two alternative approaches to the Diels\u0026ndash;Alder polymerization of tung oil. RSC Adv. 4 (2014) 26829\u0026ndash;26837.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC. Guangxue, G. Xiaoyuan, X. Ruixin, et al., Synthesis and characterization of UV-curable castor oil-based polyfunctional polyurethane acrylate via photo-click chemistry andisocyanate polyurethane reaction. Prog. Org. Coat. 93 (2016) 11\u0026ndash;16.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eB. Sara, M. Eva, J. Mats, J. Biobased UV-curable coatings based on itaconic acid. J. Coat. Tech. \u0026amp; Res. 14 (2017) 851\u0026ndash;861.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eR. Senthilkumar, M. Vijay, Development of soy-based UV-curable acrylate oligomers and study of their film properties. Prog. Org. Coat. 76 (2013) 78\u0026ndash;85.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA.C. Fonseca, I.M. Lopes, J.F.J. Coelho, et al., Synthesis of Unsaturated Polyesters Based on Renewable Monomers: Structure/Properties Relationship and Crosslinking with 2-Hydroxyethyl Methacrylate. React. Funct. Poly. 97 (2015) 1\u0026ndash;11.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eL. Ren, L. Jing, A. Sharonie, et al., High biocontent natural plant oil based UV-curable branched oligomers. Prog. Org. Coat. 105 (2017) 143\u0026ndash;148.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS. Allauddin, R. Narayan, K.V.S.N. Raju, Synthesis and Properties of Alkoxysilane Castor Oil and Their Polyurethane/Urea\u0026ndash;Silica Hybrid Coating Films. ACS Sust. Chem. \u0026amp; Eng. 1 (2013) 910\u0026ndash;918.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS. Allauddin, S. Varaprasad, S. R. Thumu, et al., One-pot synthesis and physicochemical properties of high functionality soy polyols and their Polyurethane-Urea coatings. Industrial Crops \u0026amp; Products 85 (2016) 361\u0026ndash;371.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS.R. Ivan, B. Jaroslava, K. Ivan, et al., The properties of polyurethane hybrid materials based on castor oil. Mat.Chem. Phy. 1 (2012) 74\u0026ndash;81.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eP. Tran, D. Graiver, R. Narayan, Ozone-mediated polyol synthesis from soybean oil.J. Am. Oil Chem. Soc. 82 (2005) 653\u0026ndash;659.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eF. Pion, K.K. Jena, S. Allauddin, et al., Preparation and Characterization of Waterborne Hyperbranched Polyurethane-Urea and Their Hybrid Coatings. Ind. Eng. Chem. Res. 49 (2010) 4517\u0026ndash;4527.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX. Kong, G. Liu, J.M. Curtis, Novel polyurethane produced from canola oil based poly(ether ester) polyols: Synthesis, characterization and properties. Eur. Poly. J. 48 (2012) 2097\u0026ndash;2106.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eI. Javni, Z.S. Petrović, A. Guo, R. Fuller, Thermal stability of polyurethanes based on vegetable oils. J. Appl. Polym. Sci. 8 (2000) 1723\u0026ndash;1734.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eE. Hablot, D. Zheng, M. Bouquey, L. Av\u0026eacute;rous, Polyurethanes based on Castor Oil: Kinetics, Chemical, Mechanical and Thermal Properties, Macro. Mat. Eng. 293 (2008) 922\u0026ndash;929.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ.H. Chen, D.D. Hu, Y.D. Li, et al. Castor oil derived poly (urethane urea) networks with reprocessibility and enhanced mechanical properties. Polymer 143 (2018) 79\u0026ndash;86.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Schemes","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-polymer-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jpol","sideBox":"Learn more about [Journal of Polymer Research](https://www.springer.com/journal/10965)","snPcode":"10965","submissionUrl":"https://www.editorialmanager.com/jpol/","title":"Journal of Polymer Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"castor oil, maleic anhydride, polyurethane, swelling, glass transition, thermal","lastPublishedDoi":"10.21203/rs.3.rs-5260042/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5260042/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe present work to study the impact of substituting the HEMA monomer in the synthesis of acrylic polyols with a bio-based free radical hydroxyl functional macromonomer derived from castor oil (CO). It also evaluates the coating properties of the resulting polyurethanes (PUs) in comparison to conventional acrylic polyols (AP-HEMA) derived from HEMA. To achieve this, castor oil was first reacted with maleic anhydride (MA) to produce the castor oil-derived free radical polymerizable hydroxyl functional macromonomer (COMA). Subsequently, castor oil-based acrylic hybrid polyols were synthesized using acrylate monomers, specifically methyl methacrylate (MMA) and butyl acrylate (BA), along with varying weight percentages of COMA through a conventional radical copolymerization process. The successful replacement of HEMA with COMA in the acrylic polymerization was confirmed through Fourier transform infrared (FTIR) spectroscopy, hydroxyl value analysis, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The acrylic hybrid polyols derived from castor oil exhibit reduced viscosity, lower glass transition temperature (Tg), and diminished molecular weight when compared to AP-HEMA. Both types of resins, namely the castor oil-based and AP-HEMA, underwent further reaction with Isophorone diisocyanate (IPDI) at an OH: NCO ratio of 1:1.6, resulting in isocyanate-terminated polyurethane pre-polymers. The Tg of the castor oil-based acrylic hybrid polyurethane coating films was observed to be lower than that of petroleum-derived HEMA-based acrylic polyols, demonstrating enhanced performance in terms of contact angle, water resistance, flexibility, adhesion, and abrasion resistance. The overall findings suggest that the bio-derived free radical polymerizable hydroxyl functionality possesses a polymerization tendency within the conventional acrylic polymerization framework, indicating its potential as a substitute for the HEMA monomer in the synthesis of acrylic polyols, thereby yielding high solid content resins suitable for high-performance polyurethane coating applications.\u003c/p\u003e","manuscriptTitle":"Effective Studies of bio-derived free radical polymerizable hydroxyl functional Macromonomer for replacement of Hydroxyl Ethyl Methacrylate (HEMA) in acrylic polyols and their Polyurethane-Urea Coatings","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-11-08 15:13:54","doi":"10.21203/rs.3.rs-5260042/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2024-11-18T12:07:28+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-10-29T04:08:11+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Journal of Polymer Research","date":"2024-10-21T22:06:40+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-10-18T01:15:07+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Polymer Research","date":"2024-10-17T01:19:24+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-polymer-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jpol","sideBox":"Learn more about [Journal of Polymer Research](https://www.springer.com/journal/10965)","snPcode":"10965","submissionUrl":"https://www.editorialmanager.com/jpol/","title":"Journal of Polymer Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"9e15b0c7-898f-458a-8ef2-73df6b6154af","owner":[],"postedDate":"November 8th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-02-17T16:03:34+00:00","versionOfRecord":{"articleIdentity":"rs-5260042","link":"https://doi.org/10.1007/s10965-025-04295-2","journal":{"identity":"journal-of-polymer-research","isVorOnly":false,"title":"Journal of Polymer Research"},"publishedOn":"2025-02-15 15:57:53","publishedOnDateReadable":"February 15th, 2025"},"versionCreatedAt":"2024-11-08 15:13:54","video":"","vorDoi":"10.1007/s10965-025-04295-2","vorDoiUrl":"https://doi.org/10.1007/s10965-025-04295-2","workflowStages":[]},"version":"v1","identity":"rs-5260042","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5260042","identity":"rs-5260042","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}