Design of Rectifiable Bio-based Polybenzoxazine for Stimulated Self-Healing and Shape Memory applications with antimicrobial activity

Design of Rectifiable Bio-based Polybenzoxazine for Stimulated Self-Healing and Shape Memory applications with antimicrobial activity | 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 Design of Rectifiable Bio-based Polybenzoxazine for Stimulated Self-Healing and Shape Memory applications with antimicrobial activity A Revathi, Krishnamoorthy Krishnadevi, V Anuradha, D Ramachandhran This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3616016/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Jun, 2024 Read the published version in Journal of Polymer Research → Version 1 posted 5 You are reading this latest preprint version Abstract Worldwide, recycling of bio-waste into fixable self-healing materials is a big challenge, in this paper, a feasible approach used for to synthesis partially bio-based benzoxazine from cashew nut shells. Melamine, cardanol and paraformaldehyde have been used to develop bio-based benzoxazine monomer through the Mannich condensation reaction, which is then thermally co-polymerized with 2-Mercaptoethanol and Polyurethane. The structure of the monomer and composites have been confirmed by using traditional spectroscopy techniques. Our modified bio-based polybenzoxazine showed good self-healing and shape memory properties. The duration of the recovery process was significantly influenced by the thiol and polyurethane unit. The self-healing property of Poly(SH- co -CDL-m) Poly(U1/SH- co -CDL-m), Poly(U2/SH-co-CDL-m) was investigated with Scanning Electronic Microscopy analysis and Optical Microscopy analysis. Finally, the resultant bio-based CDL-m polybenzoxazine, which is achieved the goal of cleaner production by using biomass and reducing petrochemical recourses, production and energy emission. Polymer matrix composites Recycling Self-healing Anti-microbial Shape memory Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 1. Introduction Self-healing and shape memory polymers were smart materials, the capability of a material to recover from physical damage, break, corrosion, cut or fracture and can return to their original state causing their own repair followed by change their intrinsic shape to form a temporary shape under certain conditions and converted into their original shape by external triggers such as light, temperature, humidity, and so on [1–4] . The self-healing and shape memory smart polymers have extensive applications inclusive of microcapsules [5–7] , aerospace, sensors, bio-medicine and vascular channels [8] . The major drawback of the self-healing and shape memory smart polymers were must be light weight, environment friendly, anti-microbial in nature and feasible developmental methods. Generally, shape memory and self-healing polymeric materials were prepared from the petroleum-based resins and creating environmental issues. Consequently, the current trend in the smart polymer development is to introduce the greener monomers [9] for the production of light weight polymers. Polybenzoxazine was a polymeric material that consists of benzoxazine monomers and has many applications [10,11] in different fields such as engineering, medicine, aerospace and packing industries. Unlike other polymers, polybenzoxazine does not undergo degradation at high temperature and illustrate an excellent choice for high-temperature processing and storage applications [12–15] . The benzoxazine polymeric materials were facing the problem in choice of raw materials from petroleum resources. At the same time the development of eco-friendly polymeric materials has been brought into a main consideration because of the maximum usage of petroleum based polymeric monomers and their environmental issues. Therefore, development of bio-based polymeric materials from renewable resources was highly desired, which aims to satisfy the future sustainable development [1,16,17]. Bio-based materials were also desired in order to reduce our carbon footprint. Researchers have made great efforts on producing new generation of bio-based polymers, which are capable of competing with the traditional polymers based on petrochemistry [ 18,19 ]. Numerous sustainable phenolic sources have been used for to synthesis a bio-based benzoxazine monomer such as eugenol [11] , chavicol [20] , vanillin [ 21,22 ], urushiol [ 23,24 ], resveratrol [ 25 ], guaiacol [26,27] , cinnamic/cinnamates [ 28 ], coumarin [ 29 ], etc., The sustainable and recyclable benzoxazines, obtained from the abundant bio-waste with low cost of raw materials serve as excellent substitutes for synthetic monomer. The one of the bio-waste phenolic sources was cardanol and occurred from cashew nut shell consist of an unsaturated alkyl chain [ 30–32 ] and the presence of an unsaturated alkyl chain in cardanol was used to produce a variety of products [ 33,34 ]. Cardanol was an alternative to fossil fuels and can be used as an alternative for the production of plastics and other industrial products [ 18 ]. The bio-based polybenzoxazine have fewer thermal properties and have been overcome by use of thermally stable aromatic amines. Melamine(1,3,5-triazine-2,4,6-triamine) was a chemical compound that was used in a variety of industrial and commercial applications. Also used as an additive to plastics as a flame retardant [ 35 ] material. Melamine was a trisubstituted amine and resistant to heat and corrosion, stable at high temperatures. In the present study, developing and designing recyclable bio-based Polybenzoxazine for Stimulated Self-Healing and Shape Memory applications with antimicrobial activity through a feasible method. By utilizing tri-substituted cardanol melamine based benzoxazine co-polymerized with different weight percentage of Mercaptoethanol and Polyurethanes. The self-healing and shape memory Properties of bio-based polybenzoxazine compounds were studied by different analytical methods like SEM and Optical microscopy techniques. The antimicrobial activities were analysed by using MTT assay. Results obtained from different studies were to be same, analysed and reported. 2. Experimental Part 2.1. Materials Melamine (99%), 2-Mercaptoethanol and Hexamethylene diisocyanate were purchased from Sigma Aldrich, India. Paraformaldehyde and other solvents like Ethyl acetate, Chloroform (AR grade) were purchased form SRL Chemicals, India. Cardanol was procured from Sathya cashew chemicals Pvt. Ltd. Chennai, India. 2.2. Benzoxazine Monomer Preparation Cardanol-Melamine benzoxazine (CDL-m) monomer was prepared as per our previous report [ 36 ] (Scheme 1 ) by mixing of 0.03 moles of melamine in 100mL of 1:1 ratio of methanol and de-ionized water. 0.2 moles of paraformaldehyde were added and stirred at room temperature, later 0.03 and the temperature of the reaction was gradually increased 85˚C. Maintain the temperature at 110˚C for overnight with stirring. The formed CDL-m benzoxazine was extracted with chloroform and washed with 0.5 N sodium bicarbonate and three times with de-ionized water. Solvent was evaporated in oven at 40˚C overnight. Dark brown colour CDL-m benzoxazine monomer liquid was formed and confirmed by using 1 H NMR [ 36 ]. 2.3. Process of Polymerization Prepared CDL-m benzoxazine was polymerized with 2-Mercaptoethanol and Hexamethylene diisocyanate in the ratio of 1, 1:0.5, 1:0.5:0.25, 1:0.5:0.5 (Table 1 ) respectively. The renewable tri-substituted cardanol melamine based benzoxazine co-polymerized with different weight percentage of Mercaptoethanol and Polyurethanes (Scheme 2 ) were thoroughly mixed with efficient agitation and then they were separately poured into a silane coated glass plate and cured at 50°C, 70°C, 90°C, 110°C, 130°C, 150°C, 170°C, 190°C, 210°C for 1 h each and post cured at 220°C for 2 h to get bio-composites and utilized for further studies. The cured product was coded as Poly(CDL-m), Poly(SH- co -CDL-m), Poly(U1/SH- co -CDL-m), Poly(U2/SH- co -CDL-m) respectively. Table 1 Weight percentage of Poly(CDL-m), Poly(SH- co -CDL-m), Poly(U1/SH- co -CDL-m), Poly(U2/SH- co -CDL-m) Sample Code CDL-m(%) SH(%) PU(%) Solvent THF(mL) Poly(CDL-m) 100 - - 1 Poly(SH- co -CDL-m) 100 50 - 1 Poly(U1/SH- co -CDL-m) 100 50 25 1 Poly(U2/SH- co -CDL-m) 100 50 50 1 2.4. Characterization Thermogravimetric analysis (TGA) was performed on Netzsch STA 409 thermogravimetric analyser (Germany) under a continuous flow of nitrogen (20 mL min − 1 ) instrument at a heating rate of 10˚C min − 1 . Differential scanning calorimetric (DSC) analysis was performed on Netzsch DSC-200 analyser. All the samples (about 10mg in weight) were recorded at a heating rate of 10˚C min − 1 . Fourier transform infrared (FTIR) spectra were recorded on the PerkinElmer 6X spectrometer (Waltham, Massachusetts, USA). The shape memory properties of Poly(U1/SH-co-CDL-m), Poly(U2/SH-co-CDL-m) was studied with Bending-Recovery experiments at 20˚C, 2 minutes. Scanning electron microscopy (SEM) of polymerized/cured resins was investigated with SEM-VEGA3 TESCAN and Optical microscopy (Zeiss lsm 700). MTT assay was inspected at Pondicherry Centre for Biological Science and Educational Trust. Self-healing property was identified at 50˚C and 25˚C temperature. 2.5. Cell culture and MTT assay: The human liver cancer cell line (Hep3B) was plated separately using 96 well plates with the concentration of 1×10 4 cells/well in DMEM media with 1X Antibiotic Antimycotic Solution and 10% fetal bovine serum (Himedia, India) in CO 2 incubator at 37˚C with 5% CO 2 . The cells were washed with 200 ul of 1X PBS, then the cells were treated with various test concentrations of sample A and IC50 of Doxorubicin as aspirated from cells at the end of the treatment period. 0.5mg/mL MTT prepared in 1X PBS was added and incubated at 37˚C for 4 h using CO 2 incubator. After incubation period, the medium containing MTT was discarded from the cells and washed using 200 uL of PBS. The formed crystal was dissolved with 100 uL of DMSO and thoroughly mixed. The development of colour intensity was evaluated at 570nm. The formazan dye turns to purple blue colour [ 37,38,39 ] The absorbance was measured at 570 nm using microplate reader [ 40,11 ]. 3. Results and Discussion 3.1.a. Structural Confirmation of bio-based trisubstituted benzoxazine monomer: The FTIR spectra of CDL-m benzoxazine monomer was shown in Fig. 1 . According to spectra, the bands at 1561 cm − 1 and 1457 cm − 1 could be assigned to 1,2,4-tri-substituted benzene ring in the CDL-m. The bands appearing at 1150 cm − 1 and 1354 cm − 1 were attributed to symmetric stretching of C-O-C and asymmetric stretching of Ar-O-C of benzoxazine and 1080 cm − 1 was for C-O stretching of polyether domain are visible. The band at 923 cm − 1 was confirms the benzoxazine ring formation. The bands at 2924 cm − 1 and 2853 cm − 1 could be assigned to symmetric and asymmetric stretching of methylene groups in cardanol moiety respectively. In the same way, FTIR spectrum was taken for bio-based polybenzoxazine co-polymerized with Mercaptoethanol and Hexamethylene diisocyanate with different weight ratios. Figure 1 shows FTIR spectra of Poly(CDL-m), Poly(SH- co -CDL-m), Poly(U1/SH- co -CDL-m) and Poly(U2/SH- co -CDL-m) and the disappearance of oxazine ring peak at 923 cm − 1 confirms the complete ring-opening polymerization of oxazine. The new bands appeared at 794 cm − 1 to 802 cm − 1 indicates the existence of C-S-C bonds. 1248 cm − 1 and 1529 cm − 1 , these two new bands represent the N─H bending vibration and C─N stretching vibration corresponds to the addition of urethane to the CDL-m. The appearance of a band at 1701 cm − 1 shows the C═O stretching vibrations and also the band at 3334 cm − 1 show the N─H stretching due to the urethane linkage in the CDL-m. 3.1.b. NMR spectra of CDL-m: The synthesised CDL-m monomer structure was confirmed by the Nuclear Magnetic Resonance Spectroscopy. Figure 2 shows the NMR spectra of CDL-m from the results, the aromatic proton peaks were appeared at 6.8 and 7.2 ppm. The benzoxazine ring moiety peaks was occurred for O─CH 2 ─N at 5.9 ppm and ph─CH 2 ─N for 4.5 ppm [36]. The aliphatic chain protons of cardanol were appeared at 1.23, 1.39, 1.59 and 2.51 ppm. Followed by the unsaturated double bond of cardanol was appeared at 4.4–6.2 ppm. 3.2. Curing temperatures of (CDL-m), (SH- co -CDL-m), (U/SH- co -CDL-m) : The curing temperature of cardanol-melamine monomer followed by SH and polyurethane fused monomers of (CDL-m), (SH- co -CDL-m), (U/SH- co -CDL-m) was investigated with DSC thermogram and was shown in Fig. 3 . The exothermic peaks (T p ) appeared at 229, 213, 169 for CDL-m, (SH- co -CDL-m) and (U/SH- co -CDL-m) monomers respectively, and confirms the ring opening polymerization temperature of cardanol based benzoxazine was at 250˚C [ 36 ]. The curing temperatures was gradually decreased after addition of SH and PU in the CDL-m due to the presence of acidic hydrogen in thiol moiety and allylic side chain in polyurethane moiety consist the T i peak was appeared at 216. 209 and 149 for CDL-m, SH- co -CDL-m and U/SH- co -CDL-m respectively. 3.3. Thermogravimetric Analysis: Thermal behaviour of poly(CDL-m) was investigated by DSC and TGA analysis. Generally, The CDL-m monomer under goes ring opening polymerization at 230˚C [ 36 ]. The polymerization temperature was reported to be higher due to the melamine core and steric hinderance brought by the side chain. The thermal decomposition temperature results of (Fig. 4 ) Poly(CDL-m), Poly(SH- co -CDL-m), Poly(U1/SH- co -CDL-m), Poly(U2/SH- co -CDL-m) was listed in Table 2 . From the results, the degradation temperature of Poly(SH- co -CDL-m) was much higher than those of existing isocyanide co-polymerized polybenzoxazine due to the presence of thiol unit.[ 41,1 ] Simultaneously degradation temperature and the char yield value decreasing when increasing the percentage of isocyanide into the material because of the presence of soften group of urethane linkage.[ 41,1 ] At the same time char yield values were less for neat because of the presence biobased aliphatic chain after the incorporation of thiol unit and the presence of free SH group in the bio-based composites the char yield value increases. Table 2 Thermal properties of Poly(CDL-m),Poly(SH- co -CDL-m),Poly(U1/SH- co -CDL-m),Poly(U2/SH- co -CDL-m). Samples Tg°C 5 wt.% 10 wt.% Max. wt.% Char yield % at 800˚C Poly(CDL-m) 216 229 257 299 8 Poly(SH- co -CDL-m) 268 290 314 357 24 Poly(U1/SH- co -CDL-m) 234 256 290 346 22 Poly(U2/SH- co -CDL-m) 225 252 289 343 21 3.4. Differential Scanning Calorimetry: The occurrence of thermal polymerization of bio-based trisubstituted benzoxazine was studied by using DSC analysis and results were shown in Table 1 and Fig. 5 . The observation of endothermic peaks appeared for all the cases of benzoxazines confirms the benzoxazine polymerization completely through thermal ring-opening mechanism. The peaks observed at 216°C, 268°C, 234°C and 225°C for Poly(CDL-m), Poly(SH- co -CDL-m), Poly(U1/SH- co -CDL-m) and Poly(U2/SH- co -CDL-m) respectively. Further, it was also observed that the curing temperature of synthesised bio-based benzoxazine trisubstituted co-polymers cured at 250°C. 3.5. Shape memory property of Poly(U2/SH- co -CDL-m): Generally, polymers exhibit two types of structural features one was reversible transition phase (original shape) which was possible when the polymer soften at above glass transition temperature and another one was temporary structure (temporary shape), formed by the external stress conditions [ 42 ]. Figure 6 shows the shape memory property of Poly(U2/SH- co -CDL-m) film. Both urethanes loaded composites showed shape memory properties but wen increasing the load of urethane linkage into the co-polymerization process the shape memory property also induced. The Fig. 6 represents the structural deformation of Poly(U2/SH- co -CDL-m) film for every 3 sec. at 40°C and the film was sized into 0.2mm × 4mm × 30mm. The Poly(U2/SH- co -CDL-m) film was bent at room temperature (temporary shape) and the shape was recovered at 40°C at 9 sec. The above structural deformation because of the presence of more hydrogen bonding like Intra and inter molecular hydrogen bonds were formed between the thiol -OH group and the Hydrogen present in the amide group of the urethane and also in between the two adjacent thiol groups of the polymer (O-H ⎢⎢⎢⎢⎢⎢⎢⎢N-H, H-S ⎢⎢⎢⎢⎢⎢⎢⎢H-N and N-H ⎢⎢⎢⎢⎢⎢⎢⎢N-H) then at certain temperature the hydrogen bonds were stimulated for the original structural deformation. 3.6. Self-healing and Recycling properties: The self-healing efficiency of Poly(SH- co -CDL-m) and recycling properties of Poly(U1/SH- co -CDL-m) loaded composites were studied and represented in Figs. 7 and 8 respectively. The Self-healing properties of the Poly(SH- co -CDL-m) composite was demonstrated in Fig. 7 . the sample was mould into heart shape and cut the heart into two pieces with help of sharp knife afterwards keep the two parts in close contact on Petri plate at 50°C for 2 h then the heart shape sample was completely healed with the help of external trigger and then repeated the cycle for three times. The self-healing efficiency of thiol loaded polybenzoxazine was due to the presence of more hydrogen bonds and external trigger of temperature. The trisubstituted cardanol melamine polybenzoxazine have different types of unsaturated aliphatic side chains and during co-polymerization with Mercaptoethanol thiol-ene reaction takes place between thiol group and double bonds. The free terminal OH group created more hydrogen bonds [ 43,44 ] and the hydrogen bond was trigger because of the external temperature and proper time interval. Figure 8 represents the recyclability of Poly(U1/SH- co -CDL-m) composites. The cross-linked polymer films of Poly(U1/SH- co -CDL-m) was grinded into a small piece, these small pieces were placed onto a Teflon sheet and pressure created with paper clamps for 2h at 50˚C. The chopped small pieces of Poly(U1/SH- co -CDL-m) film was completely reshaped, recycled and self-healed after 2 h and the repeated the above process for three times. Finally, the Poly(U1/SH- co -CDL-m) shown excellent self-healing, reshaping, recycling properties. Because of the presence of more hydrogen bond, which was formed between thiol, hydroxy and amine in urethane linkages. 3.7. Scanning Electron Microscope of Poly(SH-co-CDL-m): The self-healing efficiency of Poly(SH-co-CDL-m) was further evidenced by Scanning Electron Microscope (SEM). The Fig. 9 shows (a) damage, (b) after 2h, (c) after 4 h, (d) after 6 h, (e) after 8 h, (f) after 10 h, (g) after 24 h, and (h) after 36 h of self-healing surface for Poly(SH- co -CDL-m). The Poly(SH- co -CDL-m) composite film was damaged with a razor blade and was examined with SEM at different time intervals. Figure 9 shows very neat, clear and smooth surface of Poly(SH-co-CDL-m). The depth of the damaged surface was 1127.12 µm, 988.83 µm, 916.70 µm, 868.79 µm, 839.37 µm and 805.27 µm for damaged, after 2h, after 4 h, after 6 h, after 8 h, after 10 h of respectively for self-healing surface of Poly(SH-co-CDL-m). Later on, after 24 h the film has been completely healed without any external trigger because of the self-healing property the width of the damaged film was became reduced when increasing the time intervals. The self-healing ability of Poly(SH- co -CDL-m) was because of having chain mobility, flexibility and hydrogen bonding interactions [ 45,46 ] during self-healing process. 3.8. Optical Microscope of Poly(U1/SH-co-CDL-m): The self-healing properties was further confirmed with help of optical microscope (OM), self-healing efficiency of cross-linked polymers of Poly(U1/SH- co -CDL-m) were observed and shown in Fig. 10 . The self-healing was examined in every 1 h of time intervals and observed that the Poly(U1/SH- co -CDL-m) composite was self-healed completely within 24 h. Figure 10 (a) shows the damaged surface and Fig. 10 (e) shows the complete healing surface after 24 h due to the chain mobility, flexibility and hydrogen bonds the self-healing ability were gradually increased [ 46 ]. 3.9. MTT assay for biological properties: Cytotoxicity assays measure the ability of cytotoxic compounds to cause cell damage or cell death. To determine the cytotoxicity of the synthesised trisubstituted cardanol melamine (CDL-m) monomer was examined with MTT assay. CDL-m was used as a substrate for human liver cancer cell (Hep3B), for the investigation of cell viability and cytotoxicity. At different concentrations like Negative control, Positive control, 25 µg/ml − 1 ,50 µg/ml − 1 ,100 µg/ml − 1 ,250 µg/ml − 1 ,500 µg/ml − 1 of CDL-m was incubated in CO 2 at 37˚C with human liver cancer cells (Hep3B) for 24hr. After 24hr. the cell viability percentage was identified with MTT method. The cell viability for 25 µg/ml − 1 ,50 µg/ml − 1 ,100 µg/ml − 1 ,250 µg/ml − 1 ,500 µg/ml − 1 of CDL-m were listed as 3.98, 2.97, 1.40, 0.95, 0.94 and for Negative control 100.10 for Positive control 50.36. The results (Fig. 11 and Tables 3 & 4 ) confirm that when increasing concentration of CDL-m the cell viability was decreases. The better concentrations were 100 µg/ml − 1 ,250 µg/ml − 1 and 500 µg/ml − 1 and the mean of cell viabilities were 0.94, 0.95 and 1.04 respectively. Figure 12 shows the inhibitory concentration (IC 50 ) was 0.139 ± 0.29 µg/ml − 1 . The absorbance (OD) of CDL-m monomer with human liver cancer cell (Hep3B) was measured at 570nm with (triplet values). Table 3 The absorbance value of CDL-m with different concentrations Tested concentrations (µg/mL) OD at 570nm with (triplet values) 500 0.002 0.003 0.003 250 0.002 0.003 0.004 100 0.005 0.004 0.005 50 0.009 0.010 0.010 25 0.010 0.015 0.014 Negative control 0.327 0.333 0.322 Positive control 0.170 0.165 0.159 Table 4 The percentage of cell viability of CDL-m with different concentrations Concentration (µg/mL) % of Cell Viability Mean Standard Deviation 500 0.86 0.92 1.04 0.94 0.09 250 0.70 0.95 1.19 0.95 0.24 100 1.53 1.22 1.44 1.40 0.16 50 2.75 3.03 3.12 2.97 0.19 25 3.06 4.59 4.28 3.98 0.81 Negative control 100.00 101.83 98.47 100.10 1.68 Positive control 51.99 50.46 48.62 50.36 1.68 4. Conclusion The recyclable, re-shapable and self-healable smart polymers has been developed with biowaste trisubstituted cardanol based melamine benzoxazine co-polymerized with 2-mercaptoethanol and hexamethylene diisocyanate. The developed structure has been confirmed by FT-IR and 1 H NMR techniques. Thermal properties and curing temperature were analysed by using DSC and TGA analysis and the results confirm that the because of the presence of melamine core and aliphatic chain the thermal properties increased for monomers and in co-polymers thermal properties has been reduced due to the presence of urethane linkage. The self-healing and shape memory properties of the co-polymers have been evidenced by using SEM and optical microscope analysis and the results reveal that the composites have been self-healed and converted into original shape because of the presence of abundant hydrogen bonding along with the external trigger of temperature at 50°C. The recyclability of the polymers has been repeated three times and showed good results. The anti-microbial percentage of cell viability checked for the human liver cancer cell (Hep3B) by MTT assay and showed the inhibitory concentration (IC 50 ) was 0.139 ± 0.29 µg/ml − 1 . The developed Self-healable, recyclable and reusable polymeric material can be used for high performance industrial applications. Declarations Acknowledgement We would like to express our special thanks to VFSTR for research facilities especially CoEx-AMMPC for FT-IR, DSC, TGA, and SEM analysis. Also, we like to thanks CoEx-Bio-Technology for optical microscopy analysis. Conflict of Interest All co-authors have seen and agree with the contents of the manuscript and there is no financial interest to report. We certify that the submission is original work and is not under review at any other publication. References Sriharshitha S, Krishnadevi K, Devaraju S, Srinivasadesikan V, S L Lee. Eco-Friendly Sustainable Poly(benzoxazine- co -urethane) with Room-Temperature-Assisted Self-Healing Based on Supramolecular Interactions . ACS Omega 2020, 51(5), 33178–33185. Ling, L.; Li, J.; Zhang, G.; Sun, R.; Wong, C. 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Maehara Y, Anai H, Tamada R, Sugimachi K. The ATP assay is more sensitive than the succinate dehydrogenase inhibition test for predicting cell viability, European Journal of Cancer and Clinical Oncology . 1987 , 23(3), 273-276. Slater T, Sawyer B, Sträuli U. Studies on succinate-tetrazolium reductase systems, Biochimica. Biophysica Acta . 1963 , 77, 383-393. Florento L, Matias R, Tuaño E, Santiago K, Dela Cruz F, Tuazon A. Comparison of Cytotoxic Activity of Anticancer Drugs against Various Human Tumor Cell Lines Using In Vitro Cell- Based Approach. Int J Biomed Sci . 2012 , 8(1), 76-80. Lochab B, Shukla S, Varma I K. Naturally occurring phenolic sources: monomers and polymers, RSC Adv. 2014 , 4, 21712–21752. Xin L, Sha L Y, Guozheng L, Aijuan G. Development and Mechanism of High-Performance Fully Biobased Shape Memory Benzoxazine Resins with a Green Strategy . ACS Sustainable Chem. Eng . 2020 , 8(50), 18696–18705. Kolomiets, E.; Lehn, J.-M. Double dynamers: molecular and supramolecular double dynamic polymers, Chem. Commun . 2005 , 211, 1519−1425. Li S L, Xiao T, Wu Y, Jiang J, Wang L., New linear supramolecular polymers that are driven by the combination of quadruple hydrogen bonding and crown ether–paraquat recognition, Chem. Commun . 2011 , 47, 6903−6905. Cheng C, Zhang X, Chen X, Li J, Huang Q, Hu Z, Tu Y. Self-healing polymers based on eugenol via combination of thiolene and thiol oxidation reactions. J Polym Res . 2016 , 23, 110. Sriharshitha S, Krishnadevi K, Devaraju S, Prasanna D. Intrinsic approach of eco-friendly poly(benzoxazine co maleicanhydride) materials for self-healing applications, Journal of Polymer Research , 2022 , 29, 310. Schemes Schemes 1 and 2 are available in the Supplementary Files section Supplementary Files GA.png Scheme1.png Scheme 1: Proposed schematic representation of renewable CDL-m Benzoxazine monomer. Scheme2.png Scheme 2. Thermal curing process of CDL, Poly(CDL-m),Poly(SH- co -CDL-m),Poly(U1/SH- co -CDL-m),Poly(U2/SH- co -CDL-m). Cite Share Download PDF Status: Published Journal Publication published 01 Jun, 2024 Read the published version in Journal of Polymer Research → Version 1 posted Reviewers agreed at journal 03 Dec, 2023 Reviewers invited by journal 23 Nov, 2023 Editor invited by journal 17 Nov, 2023 Editor assigned by journal 15 Nov, 2023 First submitted to journal 14 Nov, 2023 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-3616016","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":252945922,"identity":"c1c44562-795f-415d-9eed-015ee1e4c43c","order_by":0,"name":"A Revathi","email":"","orcid":"","institution":"","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"A","middleName":"","lastName":"Revathi","suffix":""},{"id":252945923,"identity":"6126456a-30d1-4d61-b1e4-61c5b51cb3aa","order_by":1,"name":"Krishnamoorthy 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17:21:06","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":60189,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of CDL, Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composites.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/9e0bbcd186fd532630bb443d.png"},{"id":47316723,"identity":"3497cfab-139b-408b-b524-48ef4662df2d","added_by":"auto","created_at":"2023-11-29 17:29:06","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":45813,"visible":true,"origin":"","legend":"\u003cp\u003eNMR Spectrum of CDL-monomer\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/fd44b39c30da20059f2ba8d7.png"},{"id":47316270,"identity":"b625e5ad-7708-4da6-ba12-f0770d460ed4","added_by":"auto","created_at":"2023-11-29 17:21:06","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":33065,"visible":true,"origin":"","legend":"\u003cp\u003eCuring temperatures of (CDL-m) monomer and (SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), (U/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) co-monomers.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/4183240476203b63ef7e5d8c.png"},{"id":47316721,"identity":"e1cc8dbb-87d8-4895-98b5-ed120f548f23","added_by":"auto","created_at":"2023-11-29 17:29:06","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":47031,"visible":true,"origin":"","legend":"\u003cp\u003eTGA curves under a Nitrogen atmosphere of Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composites.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/fe63f72eac3e293c98528afc.png"},{"id":47316271,"identity":"b2f081cf-b786-43cd-b08d-ad9f7ee46381","added_by":"auto","created_at":"2023-11-29 17:21:06","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":41650,"visible":true,"origin":"","legend":"\u003cp\u003eDSC curves of Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composites.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/af967bc77eac942451763c75.png"},{"id":47317666,"identity":"1a0c001b-afea-4572-8a66-ade6a3aa4edc","added_by":"auto","created_at":"2023-11-29 17:37:06","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":122607,"visible":true,"origin":"","legend":"\u003cp\u003eShape memory effects of Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m).\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/464628259bd0ccb846bdf31b.png"},{"id":47316725,"identity":"95e61705-f0d3-4599-a2e9-f2b2106ca299","added_by":"auto","created_at":"2023-11-29 17:29:06","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":138286,"visible":true,"origin":"","legend":"\u003cp\u003ePhotographic image of Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) showing the ability of reshaping process.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/e41e08698d96226c33a473c9.png"},{"id":47316275,"identity":"12a8a499-0229-4957-af78-1538673bbac2","added_by":"auto","created_at":"2023-11-29 17:21:06","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":131032,"visible":true,"origin":"","legend":"\u003cp\u003ePhotographic image of repeating cycle of Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composites recycling process.\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/b4a02949afb12ac48f936eb0.png"},{"id":47316284,"identity":"65afc24a-c938-47ce-9c56-e66fd22c84af","added_by":"auto","created_at":"2023-11-29 17:21:07","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":1471799,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of Poly(SH-co-CDL-m): (a) damage, (b) after 2h, (c) after 4 h, (d) after 6 h, (e) after 8 h, (f) after 10 h, (g) after 24 h, and (h) after 36 h of self-healing surface. (D-Diameter)\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/c53b8f4d8399fb9182be3c6c.png"},{"id":47316281,"identity":"ebc02257-8745-4730-b5e5-dab97c32c0c6","added_by":"auto","created_at":"2023-11-29 17:21:06","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":245577,"visible":true,"origin":"","legend":"\u003cp\u003eOptical microscope image of Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composites (a) damaged surface at 0h, (b) damaged surface at 1h, (c) damaged surface at 2h (d) damaged surface at 3h and (e) damaged surface at 24h.\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/8342851302937575fe08c8cb.png"},{"id":47316285,"identity":"8f9509a6-3219-460a-8f7c-a45e32f87141","added_by":"auto","created_at":"2023-11-29 17:21:07","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":453135,"visible":true,"origin":"","legend":"\u003cp\u003eMTT assay for staining of human liver cancer cells \u003cstrong\u003e(Hep3B) \u003c/strong\u003etreated with (a) Negative control, (b) Positive control, (c) 25 μg/ml\u003csup\u003e-1\u003c/sup\u003e, (d) 50 μg/ml\u003csup\u003e-1\u003c/sup\u003e, (e) 100\u003cstrong\u003e \u003c/strong\u003eμg/ml\u003csup\u003e-1\u003c/sup\u003e, (f) 250 μg/ml\u003csup\u003e-1\u003c/sup\u003e, (g) 500\u003cstrong\u003e \u003c/strong\u003eμg/ml\u003csup\u003e-1 \u003c/sup\u003eof CDL-m monomer.\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/a7ebef40e79690f29a73ee9a.png"},{"id":47316283,"identity":"020bb5df-74b4-431e-b3b2-8c5eb6213fcf","added_by":"auto","created_at":"2023-11-29 17:21:07","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":38931,"visible":true,"origin":"","legend":"\u003cp\u003eTest with the CDL-m monomer to determine (a) % cell viability for the control, different concentrations and (b) inhibitory concentrations (IC\u003csub\u003e50\u003c/sub\u003e) of CDL-m monomer.\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/6cb4d876b7505e6656658811.png"},{"id":58822140,"identity":"df0cc493-df41-48a8-95e8-ee94726bef51","added_by":"auto","created_at":"2024-06-21 16:33:01","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3496259,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/d21150b2-1b5f-4a01-9285-59656fc9000b.pdf"},{"id":47316722,"identity":"eade3c71-c76c-4528-832a-8213d74cc1ac","added_by":"auto","created_at":"2023-11-29 17:29:06","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":225259,"visible":true,"origin":"","legend":"","description":"","filename":"GA.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/7fe97c5d7f28e879519a6a93.png"},{"id":47316279,"identity":"79ba4f16-504b-4750-921a-654ca63cd151","added_by":"auto","created_at":"2023-11-29 17:21:06","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":35892,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1:\u003c/strong\u003e Proposed schematic representation of renewable CDL-m Benzoxazine monomer.\u003c/p\u003e","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/abd09b3d5de30c0cd8fca37f.png"},{"id":47316272,"identity":"b26f2841-7577-4b19-aeaf-029157a6119c","added_by":"auto","created_at":"2023-11-29 17:21:06","extension":"png","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":67724,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 2\u003c/strong\u003e. Thermal curing process of CDL, Poly(CDL-m),Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m),Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m),Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m).\u003c/p\u003e","description":"","filename":"Scheme2.png","url":"https://assets-eu.researchsquare.com/files/rs-3616016/v1/6237f1c7a66c6e0b0135ae64.png"}],"financialInterests":"","formattedTitle":"Design of Rectifiable Bio-based Polybenzoxazine for Stimulated Self-Healing and Shape Memory applications with antimicrobial activity","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eSelf-healing and shape memory polymers were smart materials, the capability of a material to recover from physical damage, break, corrosion, cut or fracture and can return to their original state causing their own repair followed by change their intrinsic shape to form a temporary shape under certain conditions and converted into their original shape by external triggers such as light, temperature, humidity, and so on \u003cb\u003e[1\u0026ndash;4]\u003c/b\u003e. The self-healing and shape memory smart polymers have extensive applications inclusive of microcapsules \u003cb\u003e[5\u0026ndash;7]\u003c/b\u003e, aerospace, sensors, bio-medicine and vascular channels \u003cb\u003e[8]\u003c/b\u003e. The major drawback of the self-healing and shape memory smart polymers were must be light weight, environment friendly, anti-microbial in nature and feasible developmental methods. Generally, shape memory and self-healing polymeric materials were prepared from the petroleum-based resins and creating environmental issues. Consequently, the current trend in the smart polymer development is to introduce the greener monomers \u003cb\u003e[9]\u003c/b\u003e for the production of light weight polymers.\u003c/p\u003e \u003cp\u003ePolybenzoxazine was a polymeric material that consists of benzoxazine monomers and has many applications \u003cb\u003e[10,11]\u003c/b\u003e in different fields such as engineering, medicine, aerospace and packing industries. Unlike other polymers, polybenzoxazine does not undergo degradation at high temperature and illustrate an excellent choice for high-temperature processing and storage applications \u003cb\u003e[12\u0026ndash;15]\u003c/b\u003e. The benzoxazine polymeric materials were facing the problem in choice of raw materials from petroleum resources. At the same time the development of eco-friendly polymeric materials has been brought into a main consideration because of the maximum usage of petroleum based polymeric monomers and their environmental issues. Therefore, development of bio-based polymeric materials from renewable resources was highly desired, which aims to satisfy the future sustainable development \u003cb\u003e[1,16,17].\u003c/b\u003e Bio-based materials were also desired in order to reduce our carbon footprint. Researchers have made great efforts on producing new generation of bio-based polymers, which are capable of competing with the traditional polymers based on petrochemistry [\u003cb\u003e18,19\u003c/b\u003e].\u003c/p\u003e \u003cp\u003eNumerous sustainable phenolic sources have been used for to synthesis a bio-based benzoxazine monomer such as eugenol \u003cb\u003e[11]\u003c/b\u003e, chavicol \u003cb\u003e[20]\u003c/b\u003e, vanillin [\u003cb\u003e21,22\u003c/b\u003e], urushiol [\u003cb\u003e23,24\u003c/b\u003e], resveratrol [\u003cb\u003e25\u003c/b\u003e], guaiacol \u003cb\u003e[26,27]\u003c/b\u003e, cinnamic/cinnamates [\u003cb\u003e28\u003c/b\u003e], coumarin [\u003cb\u003e29\u003c/b\u003e], etc., The sustainable and recyclable benzoxazines, obtained from the abundant bio-waste with low cost of raw materials serve as excellent substitutes for synthetic monomer. The one of the bio-waste phenolic sources was cardanol and occurred from cashew nut shell consist of an unsaturated alkyl chain [\u003cb\u003e30\u0026ndash;32\u003c/b\u003e] and the presence of an unsaturated alkyl chain in cardanol was used to produce a variety of products [\u003cb\u003e33,34\u003c/b\u003e]. Cardanol was an alternative to fossil fuels and can be used as an alternative for the production of plastics and other industrial products [\u003cb\u003e18\u003c/b\u003e]. The bio-based polybenzoxazine have fewer thermal properties and have been overcome by use of thermally stable aromatic amines. Melamine(1,3,5-triazine-2,4,6-triamine) was a chemical compound that was used in a variety of industrial and commercial applications. Also used as an additive to plastics as a flame retardant [\u003cb\u003e35\u003c/b\u003e] material. Melamine was a trisubstituted amine and resistant to heat and corrosion, stable at high temperatures.\u003c/p\u003e \u003cp\u003eIn the present study, developing and designing recyclable bio-based Polybenzoxazine for Stimulated Self-Healing and Shape Memory applications with antimicrobial activity through a feasible method. By utilizing tri-substituted cardanol melamine based benzoxazine co-polymerized with different weight percentage of Mercaptoethanol and Polyurethanes. The self-healing and shape memory Properties of bio-based polybenzoxazine compounds were studied by different analytical methods like SEM and Optical microscopy techniques. The antimicrobial activities were analysed by using MTT assay. Results obtained from different studies were to be same, analysed and reported.\u003c/p\u003e"},{"header":"2. Experimental Part","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials\u003c/h2\u003e \u003cp\u003eMelamine (99%), 2-Mercaptoethanol and Hexamethylene diisocyanate were purchased from Sigma Aldrich, India. Paraformaldehyde and other solvents like Ethyl acetate, Chloroform (AR grade) were purchased form SRL Chemicals, India. Cardanol was procured from Sathya cashew chemicals Pvt. Ltd. Chennai, India.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Benzoxazine Monomer Preparation\u003c/h2\u003e \u003cp\u003eCardanol-Melamine benzoxazine (CDL-m) monomer was prepared as per our previous report [\u003cb\u003e36\u003c/b\u003e] (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) by mixing of 0.03 moles of melamine in 100mL of 1:1 ratio of methanol and de-ionized water. 0.2 moles of paraformaldehyde were added and stirred at room temperature, later 0.03 and the temperature of the reaction was gradually increased 85˚C. Maintain the temperature at 110˚C for overnight with stirring. The formed CDL-m benzoxazine was extracted with chloroform and washed with 0.5 N sodium bicarbonate and three times with de-ionized water. Solvent was evaporated in oven at 40˚C overnight. Dark brown colour CDL-m benzoxazine monomer liquid was formed and confirmed by using \u003csup\u003e1\u003c/sup\u003eH NMR [\u003cb\u003e36\u003c/b\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Process of Polymerization\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003ePrepared CDL-m benzoxazine was polymerized with 2-Mercaptoethanol and Hexamethylene diisocyanate in the ratio of 1, 1:0.5, 1:0.5:0.25, 1:0.5:0.5 (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) respectively. The renewable tri-substituted cardanol melamine based benzoxazine co-polymerized with different weight percentage of Mercaptoethanol and Polyurethanes (Scheme \u003cspan refid=\"Sch2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) were thoroughly mixed with efficient agitation and then they were separately poured into a silane coated glass plate and cured at 50\u0026deg;C, 70\u0026deg;C, 90\u0026deg;C, 110\u0026deg;C, 130\u0026deg;C, 150\u0026deg;C, 170\u0026deg;C, 190\u0026deg;C, 210\u0026deg;C for 1 h each and post cured at 220\u0026deg;C for 2 h to get bio-composites and utilized for further studies. The cured product was coded as Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) respectively.\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\u003eWeight percentage of Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m)\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=\"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 \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\u003eCDL-m(%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSH(%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePU(%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSolvent THF(mL)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e100\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\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1\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=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Characterization\u003c/h2\u003e \u003cp\u003eThermogravimetric analysis (TGA) was performed on Netzsch STA 409 thermogravimetric analyser (Germany) under a continuous flow of nitrogen (20 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) instrument at a heating rate of 10˚C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Differential scanning calorimetric (DSC) analysis was performed on Netzsch DSC-200 analyser. All the samples (about 10mg in weight) were recorded at a heating rate of 10˚C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Fourier transform infrared (FTIR) spectra were recorded on the PerkinElmer 6X spectrometer (Waltham, Massachusetts, USA). The shape memory properties of Poly(U1/SH-co-CDL-m), Poly(U2/SH-co-CDL-m) was studied with Bending-Recovery experiments at 20˚C, 2 minutes. Scanning electron microscopy (SEM) of polymerized/cured resins was investigated with SEM-VEGA3 TESCAN and Optical microscopy (Zeiss lsm 700). MTT assay was inspected at Pondicherry Centre for Biological Science and Educational Trust. Self-healing property was identified at 50˚C and 25˚C temperature.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.5. Cell culture and MTT assay:\u003c/h2\u003e \u003cp\u003eThe human liver cancer cell line (Hep3B) was plated separately using 96 well plates with the concentration of 1\u0026times;10\u003csup\u003e4\u003c/sup\u003e cells/well in DMEM media with 1X Antibiotic Antimycotic Solution and 10% fetal bovine serum (Himedia, India) in CO\u003csub\u003e2\u003c/sub\u003e incubator at 37˚C with 5% CO\u003csub\u003e2\u003c/sub\u003e. The cells were washed with 200 ul of 1X PBS, then the cells were treated with various test concentrations of sample A and IC50 of Doxorubicin as aspirated from cells at the end of the treatment period. 0.5mg/mL MTT prepared in 1X PBS was added and incubated at 37˚C for 4 h using CO\u003csub\u003e2\u003c/sub\u003e incubator. After incubation period, the medium containing MTT was discarded from the cells and washed using 200 uL of PBS. The formed crystal was dissolved with 100 uL of DMSO and thoroughly mixed. The development of colour intensity was evaluated at 570nm. The formazan dye turns to purple blue colour [\u003cb\u003e37,38,39\u003c/b\u003e] The absorbance was measured at 570 nm using microplate reader [\u003cb\u003e40,11\u003c/b\u003e].\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.1.a. Structural Confirmation of bio-based trisubstituted benzoxazine monomer:\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe FTIR spectra of CDL-m benzoxazine monomer was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. According to spectra, the bands at 1561 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1457 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e could be assigned to 1,2,4-tri-substituted benzene ring in the CDL-m. The bands appearing at 1150 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1354 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were attributed to symmetric stretching of C-O-C and asymmetric stretching of Ar-O-C of benzoxazine and 1080 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was for C-O stretching of polyether domain are visible. The band at 923 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was confirms the benzoxazine ring formation. The bands at 2924 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 2853 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e could be assigned to symmetric and asymmetric stretching of methylene groups in cardanol moiety respectively.\u003c/p\u003e \u003cp\u003eIn the same way, FTIR spectrum was taken for bio-based polybenzoxazine co-polymerized with Mercaptoethanol and Hexamethylene diisocyanate with different weight ratios. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows FTIR spectra of Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and the disappearance of oxazine ring peak at 923 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e confirms the complete ring-opening polymerization of oxazine. The new bands appeared at 794 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 802 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e indicates the existence of C-S-C bonds. 1248 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1529 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, these two new bands represent the N─H bending vibration and C─N stretching vibration corresponds to the addition of urethane to the CDL-m. The appearance of a band at 1701 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e shows the C═O stretching vibrations and also the band at 3334 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e show the N─H stretching due to the urethane linkage in the CDL-m.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.1.b. NMR spectra of CDL-m:\u003c/h2\u003e \u003cp\u003eThe synthesised CDL-m monomer structure was confirmed by the Nuclear Magnetic Resonance Spectroscopy. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows the NMR spectra of CDL-m from the results, the aromatic proton peaks were appeared at 6.8 and 7.2 ppm. The benzoxazine ring moiety peaks was occurred for O─CH\u003csub\u003e2\u003c/sub\u003e─N at 5.9 ppm and ph─CH\u003csub\u003e2\u003c/sub\u003e─N for 4.5 ppm \u003cb\u003e[36].\u003c/b\u003e The aliphatic chain protons of cardanol were appeared at 1.23, 1.39, 1.59 and 2.51 ppm. Followed by the unsaturated double bond of cardanol was appeared at 4.4\u0026ndash;6.2 ppm.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e\u003cb\u003e3.2. Curing temperatures of (CDL-m), (SH-\u003c/b\u003e\u003cb\u003eco\u003c/b\u003e\u003cb\u003e-CDL-m), (U/SH-\u003c/b\u003e\u003cb\u003eco\u003c/b\u003e\u003cb\u003e-CDL-m)\u003c/b\u003e:\u003c/h2\u003e \u003cp\u003eThe curing temperature of cardanol-melamine monomer followed by SH and polyurethane fused monomers of (CDL-m), (SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), (U/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) was investigated with DSC thermogram and was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The exothermic peaks (T\u003csub\u003ep\u003c/sub\u003e) appeared at 229, 213, 169 for CDL-m, (SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and (U/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) monomers respectively, and confirms the ring opening polymerization temperature of cardanol based benzoxazine was at 250˚C [\u003cb\u003e36\u003c/b\u003e]. The curing temperatures was gradually decreased after addition of SH and PU in the CDL-m due to the presence of acidic hydrogen in thiol moiety and allylic side chain in polyurethane moiety consist the T\u003csub\u003ei\u003c/sub\u003e peak was appeared at 216. 209 and 149 for CDL-m, SH-\u003cem\u003eco\u003c/em\u003e-CDL-m and U/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Thermogravimetric Analysis:\u003c/h2\u003e \u003cp\u003eThermal behaviour of poly(CDL-m) was investigated by DSC and TGA analysis. Generally, The CDL-m monomer under goes ring opening polymerization at 230˚C [\u003cb\u003e36\u003c/b\u003e]. The polymerization temperature was reported to be higher due to the melamine core and steric hinderance brought by the side chain. The thermal decomposition temperature results of (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e) Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) was listed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. From the results, the degradation temperature of Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) was much higher than those of existing isocyanide co-polymerized polybenzoxazine due to the presence of thiol unit.[\u003cb\u003e41,1\u003c/b\u003e] Simultaneously degradation temperature and the char yield value decreasing when increasing the percentage of isocyanide into the material because of the presence of soften group of urethane linkage.[ \u003cb\u003e41,1\u003c/b\u003e] At the same time char yield values were less for neat because of the presence biobased aliphatic chain after the incorporation of thiol unit and the presence of free SH group in the bio-based composites the char yield value increases.\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\u003eThermal properties of Poly(CDL-m),Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m),Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m),Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSamples\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\u003e5 wt.%\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10 wt.%\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eMax. wt.%\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eChar yield % at 800˚C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e216\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e229\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e257\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e299\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e268\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e290\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e314\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e357\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e234\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e256\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e290\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e346\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e22\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePoly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e225\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e252\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e289\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e343\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e21\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 \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.4. Differential Scanning Calorimetry:\u003c/h2\u003e \u003cp\u003eThe occurrence of thermal polymerization of bio-based trisubstituted benzoxazine was studied by using DSC analysis and results were shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. The observation of endothermic peaks appeared for all the cases of benzoxazines confirms the benzoxazine polymerization completely through thermal ring-opening mechanism. The peaks observed at 216\u0026deg;C, 268\u0026deg;C, 234\u0026deg;C and 225\u0026deg;C for Poly(CDL-m), Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) respectively. Further, it was also observed that the curing temperature of synthesised bio-based benzoxazine trisubstituted co-polymers cured at 250\u0026deg;C.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Shape memory property of Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m):\u003c/h2\u003e \u003cp\u003eGenerally, polymers exhibit two types of structural features one was reversible transition phase (original shape) which was possible when the polymer soften at above glass transition temperature and another one was temporary structure (temporary shape), formed by the external stress conditions [\u003cb\u003e42\u003c/b\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows the shape memory property of Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) film. Both urethanes loaded composites showed shape memory properties but wen increasing the load of urethane linkage into the co-polymerization process the shape memory property also induced. The Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e represents the structural deformation of Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) film for every 3 sec. at 40\u0026deg;C and the film was sized into 0.2mm \u0026times; 4mm \u0026times; 30mm. The Poly(U2/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) film was bent at room temperature (temporary shape) and the shape was recovered at 40\u0026deg;C at 9 sec. The above structural deformation because of the presence of more hydrogen bonding like Intra and inter molecular hydrogen bonds were formed between the thiol -OH group and the Hydrogen present in the amide group of the urethane and also in between the two adjacent thiol groups of the polymer (O-H ⎢⎢⎢⎢⎢⎢⎢⎢N-H, H-S ⎢⎢⎢⎢⎢⎢⎢⎢H-N and N-H ⎢⎢⎢⎢⎢⎢⎢⎢N-H) then at certain temperature the hydrogen bonds were stimulated for the original structural deformation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003e3.6. Self-healing and Recycling properties:\u003c/h2\u003e \u003cp\u003eThe self-healing efficiency of Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) and recycling properties of Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) loaded composites were studied and represented in Figs.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e and \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e respectively. The Self-healing properties of the Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composite was demonstrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. the sample was mould into heart shape and cut the heart into two pieces with help of sharp knife afterwards keep the two parts in close contact on Petri plate at 50\u0026deg;C for 2 h then the heart shape sample was completely healed with the help of external trigger and then repeated the cycle for three times. The self-healing efficiency of thiol loaded polybenzoxazine was due to the presence of more hydrogen bonds and external trigger of temperature. The trisubstituted cardanol melamine polybenzoxazine have different types of unsaturated aliphatic side chains and during co-polymerization with Mercaptoethanol thiol-ene reaction takes place between thiol group and double bonds. The free terminal OH group created more hydrogen bonds [\u003cb\u003e43,44\u003c/b\u003e] and the hydrogen bond was trigger because of the external temperature and proper time interval.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e represents the recyclability of Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composites. The cross-linked polymer films of Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) was grinded into a small piece, these small pieces were placed onto a Teflon sheet and pressure created with paper clamps for 2h at 50˚C. The chopped small pieces of Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) film was completely reshaped, recycled and self-healed after 2 h and the repeated the above process for three times. Finally, the Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) shown excellent self-healing, reshaping, recycling properties. Because of the presence of more hydrogen bond, which was formed between thiol, hydroxy and amine in urethane linkages.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003e3.7. Scanning Electron Microscope of Poly(SH-co-CDL-m):\u003c/h2\u003e \u003cp\u003eThe self-healing efficiency of Poly(SH-co-CDL-m) was further evidenced by Scanning Electron Microscope (SEM). The Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e shows (a) damage, (b) after 2h, (c) after 4 h, (d) after 6 h, (e) after 8 h, (f) after 10 h, (g) after 24 h, and (h) after 36 h of self-healing surface for Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m). The Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composite film was damaged with a razor blade and was examined with SEM at different time intervals. Figure\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e shows very neat, clear and smooth surface of Poly(SH-co-CDL-m). The depth of the damaged surface was 1127.12 \u0026micro;m, 988.83 \u0026micro;m, 916.70 \u0026micro;m, 868.79 \u0026micro;m, 839.37 \u0026micro;m and 805.27 \u0026micro;m for damaged, after 2h, after 4 h, after 6 h, after 8 h, after 10 h of respectively for self-healing surface of Poly(SH-co-CDL-m). Later on, after 24 h the film has been completely healed without any external trigger because of the self-healing property the width of the damaged film was became reduced when increasing the time intervals. The self-healing ability of Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) was because of having chain mobility, flexibility and hydrogen bonding interactions [\u003cb\u003e45,46\u003c/b\u003e] during self-healing process.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003e3.8. Optical Microscope of Poly(U1/SH-co-CDL-m):\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe self-healing properties was further confirmed with help of optical microscope (OM), self-healing efficiency of cross-linked polymers of Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) were observed and shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e. The self-healing was examined in every 1 h of time intervals and observed that the Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) composite was self-healed completely within 24 h. Figure\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e \u003cb\u003e(a)\u003c/b\u003e shows the damaged surface and Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e \u003cb\u003e(e)\u003c/b\u003e shows the complete healing surface after 24 h due to the chain mobility, flexibility and hydrogen bonds the self-healing ability were gradually increased [\u003cb\u003e46\u003c/b\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec18\" class=\"Section2\"\u003e \u003ch2\u003e3.9. MTT assay for biological properties:\u003c/h2\u003e \u003cp\u003eCytotoxicity assays measure the ability of cytotoxic compounds to cause cell damage or cell death. To determine the cytotoxicity of the synthesised trisubstituted cardanol melamine (CDL-m) monomer was examined with MTT assay. CDL-m was used as a substrate for human liver cancer cell (Hep3B), for the investigation of cell viability and cytotoxicity. At different concentrations like Negative control, Positive control, 25 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,50 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,100 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,250 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,500 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of CDL-m was incubated in CO\u003csub\u003e2\u003c/sub\u003e at 37˚C with human liver cancer cells (Hep3B) for 24hr. After 24hr. the cell viability percentage was identified with MTT method. The cell viability for 25 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,50 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,100 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,250 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,500 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of CDL-m were listed as 3.98, 2.97, 1.40, 0.95, 0.94 and for Negative control 100.10 for Positive control 50.36. The results (Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e and Tables\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e \u0026amp; \u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e) confirm that when increasing concentration of CDL-m the cell viability was decreases. The better concentrations were 100 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e,250 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 500 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and the mean of cell viabilities were 0.94, 0.95 and 1.04 respectively. Figure\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e12\u003c/span\u003e shows the inhibitory concentration (IC\u003csub\u003e50\u003c/sub\u003e) was 0.139\u0026thinsp;\u0026plusmn;\u0026thinsp;0.29 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The absorbance (OD) of CDL-m monomer with human liver cancer cell (Hep3B) was measured at 570nm with (triplet values).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \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\u003eThe absorbance value of CDL-m with different concentrations\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\"\u003e \u003cp\u003eTested concentrations (\u0026micro;g/mL)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eOD at 570nm with (triplet values)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e500\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.002\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.003\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.003\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e250\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.002\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.003\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.004\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.005\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.004\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.005\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.009\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.010\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.010\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.010\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.015\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.014\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eNegative control\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003e0.327\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e0.333\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003e0.322\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePositive control\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003e0.170\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e0.165\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003e0.159\u003c/b\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 \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\u003eThe percentage of cell viability of CDL-m with different concentrations\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eConcentration (\u0026micro;g/mL)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003e% of Cell Viability\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eMean\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eStandard Deviation\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e500\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.92\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.94\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.09\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e250\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.19\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.24\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.53\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e1.40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.16\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3.12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.19\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e4.59\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e3.98\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.81\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eNegative control\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003e100.00\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e101.83\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003e98.47\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003e100.10\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003e1.68\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePositive control\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003e51.99\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e50.46\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003e48.62\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003e50.36\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003e1.68\u003c/b\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"},{"header":"4. Conclusion","content":"\u003cp\u003eThe recyclable, re-shapable and self-healable smart polymers has been developed with biowaste trisubstituted cardanol based melamine benzoxazine co-polymerized with 2-mercaptoethanol and hexamethylene diisocyanate. The developed structure has been confirmed by FT-IR and \u003csup\u003e1\u003c/sup\u003eH NMR techniques. Thermal properties and curing temperature were analysed by using DSC and TGA analysis and the results confirm that the because of the presence of melamine core and aliphatic chain the thermal properties increased for monomers and in co-polymers thermal properties has been reduced due to the presence of urethane linkage. The self-healing and shape memory properties of the co-polymers have been evidenced by using SEM and optical microscope analysis and the results reveal that the composites have been self-healed and converted into original shape because of the presence of abundant hydrogen bonding along with the external trigger of temperature at 50\u0026deg;C. The recyclability of the polymers has been repeated three times and showed good results. The anti-microbial percentage of cell viability checked for the human liver cancer cell (Hep3B) by MTT assay and showed the inhibitory concentration (IC\u003csub\u003e50\u003c/sub\u003e) was 0.139\u0026thinsp;\u0026plusmn;\u0026thinsp;0.29 \u0026micro;g/ml\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The developed Self-healable, recyclable and reusable polymeric material can be used for high performance industrial applications.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgement\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe would like to express our special thanks to VFSTR for research facilities especially CoEx-AMMPC for FT-IR, DSC, TGA, and SEM analysis. Also, we like to thanks CoEx-Bio-Technology for optical microscopy analysis.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll co-authors have seen and agree with the contents of the manuscript and there is no financial interest to report. We certify that the submission is original work and is not under review at any other publication.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eSriharshitha S, Krishnadevi K, Devaraju S, Srinivasadesikan V, S L Lee. Eco-Friendly Sustainable Poly(benzoxazine-\u003cem\u003eco\u003c/em\u003e-urethane) with Room-Temperature-Assisted Self-Healing Based on Supramolecular Interactions\u003cstrong\u003e. \u003c/strong\u003e\u003cem\u003eACS Omega\u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e 51(5), 33178\u0026ndash;33185.\u003c/li\u003e\n\u003cli\u003eLing, L.;\u0026nbsp;Li, J.;\u0026nbsp;Zhang, G.;\u0026nbsp;Sun, R.;\u0026nbsp;Wong, C. P.Self-Healing and Shape Memory Linear Polyurethane Based on Disulfide Linkages with Excellent Mechanical Property.\u0026nbsp;\u003cem\u003eMacromol.Res.\u003c/em\u003e\u003cstrong\u003e2018\u003c/strong\u003e, \u003cem\u003e2, \u003c/em\u003e365\u0026ndash;\u0026nbsp;373.\u0026nbsp;\u003c/li\u003e\n\u003cli\u003eArslan, M.;\u0026nbsp;Kiskan, B.;\u0026nbsp;Yagci, Y.Benzoxazine-based thermosets with autonomous self-healing ability.\u0026nbsp;\u003cem\u003eMacromolecules\u003c/em\u003e\u003cstrong\u003e2015,\u003c/strong\u003e \u003cem\u003e48, \u003c/em\u003e1329\u0026ndash;\u0026nbsp;1334\u003c/li\u003e\n\u003cli\u003eCao, S.;\u0026nbsp;Li, S.;\u0026nbsp;Li, M.;\u0026nbsp;Xu, L.;\u0026nbsp;Ding, H.;\u0026nbsp;Xia, J.;\u0026nbsp;Zhang, M.;\u0026nbsp;Huang, K. A.\u0026nbsp;A thermal self-healing polyurethane thermoset based on phenolic urethane.\u0026nbsp;\u003cem\u003ePolym. J.\u003c/em\u003e\u0026nbsp;\u003cstrong\u003e2017\u003c/strong\u003e, \u003cem\u003e49, \u003c/em\u003e775\u0026ndash;\u0026nbsp;781,\u003c/li\u003e\n\u003cli\u003eBrown EN, Kessler MR, Sottos NR, White SR. In situ poly(urea-formaldehyde) microencapsulation of dicyclopentadiene. \u003cem\u003eJ Microencapsul\u003c/em\u003e \u003cstrong\u003e2003\u003c/strong\u003e, 20(6), 719-30\u003c/li\u003e\n\u003cli\u003eE. N. Brown, S. R. White, N. R. Sottos, J. Mater. Microcapsule induced toughening in a self-healing polymer composite, \u003cem\u003eMaterial Sciences.\u003c/em\u003e \u003cstrong\u003e2004\u003c/strong\u003e, 39(5), 1703-1710.\u003c/li\u003e\n\u003cli\u003eKessler M. R, Sottos N. R, White S. R, Self-healing structural composite material. \u003cem\u003eA Composites Part.\u003c/em\u003e \u003cstrong\u003e2003\u003c/strong\u003e, 34(8), 743-753.\u003c/li\u003e\n\u003cli\u003eToohey K, Sottos N, Lewis J, Moor J, White, S. Self-healing materials with microvascular\u0026nbsp;networks.\u0026nbsp;\u003cem\u003eNature Mater.\u003c/em\u003e\u003cstrong\u003e2007\u003c/strong\u003e, 6, 581-585\u003c/li\u003e\n\u003cli\u003eWenwen G, Xin W, Chandra Sekhar Reddy G, Junling W, Ying P, Weiyi X, Lei S Yuan H, Cardanol derived benzoxazine in combination with boron-doped graphene toward simultaneously improved toughening and flame-retardant epoxy composites. \u003cem\u003eComposites Part A: Applied Science and Manufacturing\u003c/em\u003e. \u003cstrong\u003e2018\u003c/strong\u003e, 3, 13-23.\u003c/li\u003e\n\u003cli\u003eKiskan, N. N. Ghosh, Y. Yagci. Polybenzoxazine-based composites as high-performance materials, \u003cem\u003ePolym. Int\u003c/em\u003e., \u003cstrong\u003e2010\u003c/strong\u003e, 60(2), 167\u0026ndash;177.\u003c/li\u003e\n\u003cli\u003eSriharshitha S, Krishnadevi K, Prasanna D. 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Melamine, cardanol and paraformaldehyde have been used to develop bio-based benzoxazine monomer through the Mannich condensation reaction, which is then thermally co-polymerized with 2-Mercaptoethanol and Polyurethane. The structure of the monomer and composites have been confirmed by using traditional spectroscopy techniques. Our modified bio-based polybenzoxazine showed good self-healing and shape memory properties. The duration of the recovery process was significantly influenced by the thiol and polyurethane unit. The self-healing property of Poly(SH-\u003cem\u003eco\u003c/em\u003e-CDL-m) Poly(U1/SH-\u003cem\u003eco\u003c/em\u003e-CDL-m), Poly(U2/SH-co-CDL-m) was investigated with Scanning Electronic Microscopy analysis and Optical Microscopy analysis. Finally, the resultant bio-based CDL-m polybenzoxazine, which is achieved the goal of cleaner production by using biomass and reducing petrochemical recourses, production and energy emission.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e","manuscriptTitle":"Design of Rectifiable Bio-based Polybenzoxazine for Stimulated Self-Healing and Shape Memory applications with antimicrobial activity","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-11-29 17:21:01","doi":"10.21203/rs.3.rs-3616016/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2023-12-03T12:49:52+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2023-11-24T02:28:38+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Journal of Polymer Research","date":"2023-11-17T17:27:03+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2023-11-15T06:15:24+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Polymer Research","date":"2023-11-14T08:29:15+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":"cb151f2c-7ca8-44af-b632-fa6f044b7814","owner":[],"postedDate":"November 29th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-06-21T14:49:08+00:00","versionOfRecord":{"articleIdentity":"rs-3616016","link":"https://doi.org/10.1007/s10965-024-04009-0","journal":{"identity":"journal-of-polymer-research","isVorOnly":false,"title":"Journal of Polymer Research"},"publishedOn":"2024-06-01 14:49:08","publishedOnDateReadable":"June 1st, 2024"},"versionCreatedAt":"2023-11-29 17:21:01","video":"","vorDoi":"10.1007/s10965-024-04009-0","vorDoiUrl":"https://doi.org/10.1007/s10965-024-04009-0","workflowStages":[]},"version":"v1","identity":"rs-3616016","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3616016","identity":"rs-3616016","version":["v1"]},"buildId":"WrCJVZZCHTDjtuVLN7oU0","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}