Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from jatropha deoiled seed cake

Journal of Science: Advanced Materials and Devices xxx (2017) 1e7 Contents lists available at ScienceDirect Journal of Science: Advanced Materials and Devices journal homepage: www.elsevier.com/locate/jsamd Original Article Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake B.S Surendra a, *, M Veerabhadraswamy b a b East West Institute of Technology, Dept of Chemistry, Bangalore 560091, India Green Chemistry Center, P E S University, BSK III Stage, Bengalure 56085, India a r t i c l e i n f o a b s t r a c t Article history: Received April 2017 Received in revised form July 2017 Accepted 10 July 2017 Available online xxx We report on a two-step catalytic process, where deoiled seed cake as a feed was rapidly depolymerized and converted to a chemical intermediate under mild conditions, and a polymer compound was subsequently synthesized in the presence of an initiator under microwave irradiation 5Hydroxymethylfurfural (5-HMF) is a significant chemical intermediate compound synthesized from a deoiled Jatropha seed cake under microwave irradiation in the presence of a heterogeneous acid activated Bentonite catalyst This compound is suitable for the synthesis of polymers Our study reveals that the synthesis process is an energy-efficient and cost-effective conversion of the deoiled seed cake into the polymer compound through the bioplatform chemical intermediate The synthesized material was well characterized, confirming the formation and structures of the prepared catalysts © 2017 The Authors Publishing services by Elsevier B.V on behalf of Vietnam National University, Hanoi This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) Keywords: 5-HMF Deoiled seed cake Acid activated clay Microwave irradiation Polymer Introduction The production of fuels from non edible plant resources is extensively accepted as a sustainable alternative to petroleumderived fuels, which fulfills the increasing energy demand of the present scenario [1] According to literature, biochemical, chemical and thermochemical methods access to convert them into fuels and useful building blocks [2,3] In this sector, biodiesel from non edible plant resources like, Jatropha, Neem, Pongamia etc is one of the large-scale biofuel commodities, but during its process releasing huge amount of biowaste (seed cake) consisting of mainly polymeric carbohydrates and lignin [4], which becomes an environmental issue To overcome this problem, we have used seed cake for the synthesis of a chemical intermediate (5-HMF) and the resulting polymer Deoiled seed cake is a renewable material suitable for the production of a wide range of chemical intermediates, liquid transportation fuels, and polymers This necessitates the development of sustainable processes for conversion of biomass having carbohydrates, which forms the bridge between the growing gap for supply, demand of energy and chemicals [4] The synthesis of 5-HMF was * Corresponding author E-mail address: surendramysore2010@gmail.com (B.S Surendra) Peer review under responsibility of Vietnam National University, Hanoi catalyzed by an oxalic acid, various inorganic and organic compounds, some mineral acids such as HCl, H2SO4 and H3PO4 being employed as a homogeneous catalyzed dehydration of fructose to 5-HMF [5e10], this method suffers with low yield and separation of catalysts In order to avoid this problem, reusable or recyclable catalysts are preferred since they have increased efficiency, economic and industrial feasibility such as solid acid catalysts, ion exchange resins, zeolites, Lewis acids, clays and molecular sieves but are not limited to them [11] Among the clays, Bentonite is a mineral, which is extensively used for different applications and expressed as a hydrated aluminosilicate Bentonite contains 85% montrorillonite and the remaining components include quartz, feldspar, gypsum and other minerals [12] The preparation of a heterogeneous acid activated Bentonite clay catalyst is a significant process under microwave irradiation The microwave treatment fluctuates the physico-chemical properties like chemical composition, crystalline structure, specific surface area, particle size and the number of acidic centers [13] During the acid modification of clays, the ion exchange of aluminum in the octahedral layer can be leached out by Na, K, Fe, Mg, Zn, Cl, Li etc (Fig 1), which results in the porous material with enhanced catalytic properties Microwave-assisted synthesis has received increasing attention in recent years as a valuable alternative to the use of conductive heating for accelerating chemical reactions With no direct contact between the chemical reactants and the energy source, microwave- http://dx.doi.org/10.1016/j.jsamd.2017.07.004 2468-2179/© 2017 The Authors Publishing services by Elsevier B.V on behalf of Vietnam National University, Hanoi This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) Please cite this article in press as: B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and Devices (2017), http://dx.doi.org/10.1016/ j.jsamd.2017.07.004 B.S Surendra, M Veerabhadraswamy / Journal of Science: Advanced Materials and Devices xxx (2017) 1e7 Fig Bentonite clay activated with Hỵ assisted chemistry is energy efficient, provides fast heating rates, increased product yield, improved selectivity, and higher bulk operating temperatures and enables rapid optimization of the procedures [14] In this study, we used the modified domestic microwave ovens for the controlled synthesis of catalysts Experimental The seed cakes were collected from GKVK, Bangalore and the deoiled seed cake was obtained from Soxhlet extraction with methanol Aniline, H2SO4, Bentonite, and acetone chemicals were purchased from Sigma Aldrich fine chemicals, India, and used without further purification 2.1 Clay modification The microwave assisted preparation of an acid activated Bentonite clay catalyst by treating it with H2SO4 showed surface and acidity modification The modified clay catalysts were prepared from treating 10 g of clay with series of different concentrations of 500 ml H2SO4 (0.1 M, M, M, and M) in a round bottom flask The mixture of reactants was transferred to the microwave reactor and irradiated for 30 at 338 K, whereas a 24 h heating was required in conventional heating methods After irradiation, it was settled down and washed with water until it was free from chloride ions The obtained product was dried at 373 K for h and well grinded to get a fine powder beforeits characterization 2.2 Characterization The modified Bentonite catalysts with different concentrations were well characterized using Shimadzu Powder X-ray diffractometer (PXRD) with Cu Ka (1.541 Å) radiation with nickel filter in the 2q range 20e70 at a scan rate of 2 minÀ1 Fourier transform infrared (FT-IR) spectra of the samples were then recorded in the range 4000e500 cmÀ1 using Bruker model Alpha-P IR spectrophotometer having resolution of cmÀ1 fitted with a diamond ATR cell Acidity of the modified clay catalysts was measured by FT-IR spectroscopy using pyridine as a probe molecule The surface area was obtained by BrunnereEmmeteTeller (BET) method and the nitrogen adsorptionedesorption isotherms were carried out using Quanta chrome Nova-1000 surface analyzer at liquid nitrogen temperature The UV-Visible studies of the samples were performed in the range 200e800 nm using shimadzu spectrophotometer model UV-2600 The thermogravimetric and differential thermal (TGA-DTA) studies of the polymers were recorded in the nitrogen atmosphere at the heating range 200e1400  C using SDT Q600 V20 2.3 Polymer synthesis via 5-HMF intermediate using Jatropha deoiled seed cake Non edible deoiled seed cake sample (50 g) in acetone (100 ml) was heated in the presence of an acid modified catalyst (1 g) at 338 K The reaction mixture was then transferred to the microwave reactor and irradiated for 30 The obtained filtrate (dark brownish color liquid) indicates the presence of 5-HMF intermediate compound and it was confirmed by gas chromatography mass spectra (GCeMS), FT-IR and UV-Visible analyses The synthesized 5HMF intermediate compound is in an unstable, liquid form at room temperature and consumes more time for its separation Therefore, it can easily convert from the liquid state to solid derivatives of 5HMF when treated with different monomers like acrylamide, acrylonitrile, ethylacrylate, and methylacrylate in the presence of an initiator ammonium per sulfate and a pinch of sodium lauryl sulfate, resulting in the polymer The synthesized 5-HMF polymer products were analyzed by TGA-DTA and FT-IR techniques The possible reactions of the 5-HMF polymer as illustrated in Scheme Results and discussion 3.1 Characterizations of synthesized acid modified clay catalysts 3.1.1 PXRD analysis PXRD patterns showed determination of the crystallinity and phase composition of the synthesized acid activated clay catalysts via the microwave heating route (Fig 2) The diffraction peaks indexed as (110), (130), (200) and (060) were well matched with JCPDS card number 1985 [15] These samples consisted of predominantly montmorillonite, substantial amounts of quartz, feldspar and gypsum impurities During the modification of the clay catalyst, the ion exchange reaction with sulfuric acid appeared to occur in the octahedral layer of the clay sample, leading to variation of the structural parameters, forming porosity and enhancing catalytic properties These maximum inter-allocation ions were observed in the case of M H2SO4 catalyst, which involves changing physicochemical properties of the clays specifically the surface pores with decrease in size resulting in the increased surface area and pore volume under a microwave treatment [16] Thus, the crystallization process proceeded along (110) crystal plane and the intensity of the plane was found to be maximum for M compared to 0.1 M, M and M H2SO4 activated clays The crystallite sizes estimated by Scherer's method [17,18] were in the range 12e18 nm for different concentrations of H2SO4 synthesized from microwave heating 3.1.2 FT-IR analysis Fig shows the FTIR spectra with the identification of various functional groups present in the acid activated Bentonite clay with Please cite this article in press as: B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and Devices (2017), http://dx.doi.org/10.1016/ j.jsamd.2017.07.004 B.S Surendra, M Veerabhadraswamy / Journal of Science: Advanced Materials and Devices xxx (2017) 1e7 Scheme Polymerization of 5-HMF with different monomers (acrylamide, acrylonitrile, ethylacrylate and methylacrylate) different concentrations (0.1 M, M, M, and M Hỵ) The SieO stretching vibrations were observed at 798 cmÀ1, 620 cmÀ1, and 526 cmÀ1 showing the presence of quartz The strong absorption bands at ~1100e1000 cmÀ1 and the most intensive band at 1036 cmÀ1 is attributed to SiÀO stretching A strong band at 3640 and 3154 cmÀ1 indicates the possibility of the stretching vibration of the hydroxyl groups of montmorillonite coordinated to octahedral Al3ỵ cations [19] The bands at 917 and 798 cmÀ1 corresponding to the AlAlOH and AlMgOH bending vibrations were observed respectively The band 620 cmÀ1 indicates MÀO vibrations, attributed to the coupled AlÀO and SiÀO stretching frequencies [20,21] 3.1.3 SEM analysis The SEM micrographs of the acid modified Bentonite clay catalysts at different magnifications are shown in Fig In the microwave heating method, heat energy plays a vital role in preparing the modified clay catalysts via a simple and quick synthesis route Thus, the acid allocation into the Bentonite interior followed by the substituting of ions, forming a dense collections of the acid activated clay [22] After the modification of clay, the surface seems to be distressed by the grinding process and acid activation process [23] This is reliable with the increase in surface area after the acid allocation into the material Please cite this article in press as: B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and Devices (2017), http://dx.doi.org/10.1016/ j.jsamd.2017.07.004 B.S Surendra, M Veerabhadraswamy / Journal of Science: Advanced Materials and Devices xxx (2017) 1e7 Fig The PXRD patterns of the raw bentonite and acid activated Bentonite samples (M ¼ montmorillonite; Cr ¼ cristobalite; Q ¼ quartz; F ¼ feldspar) Fig FT-IR spectra of the acid activated Bentonite clay catalysts 3.1.4 BET analysis The surface area, porosity and textural properties of the synthesized clay and the untreated raw Bentonite particle have been determined by the BET method using liquid nitrogen (77 K) as an adsorbent gas (Fig 5) The surface area is one of the important parameters to characterize powder samples related to other parameters such as particle size, shape, surface textures, size distribution, density and open porosity with in agglomerated particles [24] The microwave heating derived products usually have a large surface area due to liberation of heat (exothermicity) During microwave reaction the temperature is just enough to form nuclei but too short for grain growth The increase in the surface area and pore volume with increase in the strength of H2SO4 The BET surface area and average pore diameter of acid treated (0.1 M, M, M, M) and untreated raw Bentonite samples were found to be 16.21, 18.21, 60.40, 30.28 and 21.10 m2/g and 98.40, 86.04, 71.21, 86.31 and 133.13 Å, respectively The large surface area and porous nature of the prepared samples were due to uniform distribution of particles as observed in SEM images Fig Nitrogen adsorption and desorption isotherms and pore volume distribution curve (inset) of Raw Bentonite and acid activated Bentonite Fig SEM images of 0.1 M H2SO4 (a & e), M H2SO4 (b & f), M H2SO4 (c & g) and M H2SO4 (d & h) modified clays Please cite this article in press as: B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and Devices (2017), http://dx.doi.org/10.1016/ j.jsamd.2017.07.004 B.S Surendra, M Veerabhadraswamy / Journal of Science: Advanced Materials and Devices xxx (2017) 1e7 3.2 5-HMF synthesis from Jatropha deoiled seed cake The insitu production of 5-HMF from the acid hydrolysis of deoiled seed cakes (lignocelluloses and carbohydrates) was done using acid modified Bentonite clay under microwave irradiation The peak at 283 nm in UV-Visible spectra [Fig (a)] indicates the formation of a 5-HMF chemical intermediate [25,26] The qualitative and quantitative analysis of 5-HMF were done by GCeMS The percentage yield (34%) of 5-HMF was calculated from the GCeMS mass chromatogram as shown in Fig (b) The 5-HMF intermediate was further confirmed by FTIR spectroscopy, the sharp band at 1667 cmÀ1 was assigned to the stretching vibration of C]O (carbonyl group); the absorbance at 1072 cmÀ1 indicates the presence of CeO stretching vibration The absorbance at 2851 & 2932 cmÀ1 was attributed to the presence of methylene group (eCH2 e) and its bending vibrational band was found at 1460 cmÀ1 The presence of free hydroxyl groups in 5-HMF was observed at 3405 cmÀ1 as shown in Fig 6(c) [27] and the detailed values were given in Table Table FTIR absorption bands for functional groups present in 5-HMF SL no Type of vibration Wave number (cmÀ1) OH board band CH2 stretching band C¼O CH2 CeO vibration CH2 vibration 3405 2932,2851 1667 1460 1072 842,698 3.3 Polymer synthesis from 5-HMF 5-HMF as a renewable platform chemical intermediate and has wide applications in the field of reduction, oxidation, condensation reaction etc The microwave assisted insitu polymerization of 5HMF was achieved with different acrylates (acrylamide, acrylonitrile, ethylacrylate and methylacrylate) in the presence of ammonium per sulfate and sodium lauryl sulfate Thermal study on the obtained polymer in a controlled nitrogen atmosphere was carried Fig Analysis of 5-HMF from a) GCeMS, b) UVeVisible and c) FT-IR spectra Please cite this article in press as: B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and Devices (2017), http://dx.doi.org/10.1016/ j.jsamd.2017.07.004 B.S Surendra, M Veerabhadraswamy / Journal of Science: Advanced Materials and Devices xxx (2017) 1e7 out to understand the weight loss and thermal stability These measurements were used mainly to determine the thermal or oxidative stabilities of materials The results obtained indicate either weight loss or gain due to decomposition, oxidation or loss of volatiles (such as moisture) The most probable decomposition pattern of the polymer is proposed on the basis of the TGA peak temperature of all the polymers The TGA peak temperature of these polymers indicates that the decomposition of the polymer moiety in different stages The thermal decomposition processes of the polymers show one water loss event (up to 200  C), and two main events at the temperature of maximum decomposition (Tm) in the ranges of 200e360 and 380e500  C (Fig 7) The event at around 300  C is attributed mainly to the loss of CO2 Depolymerization, decarbonylation and the evolution of the products containing OeH, CeH, C]O, CeC and CeO also occurred, but to a lesser extent In the temperature range around 400  C, the events are due to the pyrolytic decomposition of carbonaceous materials formed during the degradation of the 5-HMF polymer compounds The significant weight loss in the range 310e700  C in the TG curves showed the high thermal degradation, due to formation of volatiles in the course of heating up for pyrolysis The percentage degradation of polymer at a specific temperature reported in Table FT-IR spectra of the polymer compounds obtained from different monomers are shown in Fig It can be observed that the bands at 3251 cmÀ1 for primary amines (NeH stretching) and 1667 cmÀ1 for C]O stretching indicated presence of the amide functional group [28], while the bands at 2945 cmÀ1 and 2844 cmÀ1 showed CeH stretching vibrations [29] The bending vibration of CeH in CH3 group showed at 1435 cmÀ1 and 1218e1054 cmÀ1 for the bending Fig FT-IR spectra of polymer compounds: acrylamide, acrylonitrile, ethylacrylates and methylacrylate mode of CeN amines In an acrylonitrile-HMF polymer, the bands at 2919 and 2858 cmÀ1 indicated the CeH stretching vibration, 2243 cmÀ1 for nitrile stretching and the band at 1453 cmÀ1 represented the bending vibrations of CH2 group The stretching vibrations of carbonyl (C]O) group at 1655 cmÀ1 and their bending vibration at 1220 and 1056 cmÀ1 were also observed EthylacrylateHMF polymer showed the CeH stretching band with peaks at 2923 Fig (a & b) TGA-DTA studies of polymers like acrylamide, acrylonitrile, ethylacrylates and methylacrylate Table The percentage degradation or weight loss of polymers under specific temperature SL no Samples Weight (mg) Temperature ( C) Weight loss (%) 1) Poly2-[(5-ethylfuran-2-yl)oxy] propanamide 100 2) Poly3-{[5 (hydroxymethyl)furan-2-yl]methoxy}propanenitrile 100 3) Polyethyl 3-{[5 (hydroxymethyl)furan-2-yl]methoxy}propanoate 100 0e700 700e780 0e191 200e680 0e340 340e680 4) Polyethyl 3-{[5 (hydroxymethyl)furan-2-yl]methoxy}propanoate 100 5) Polyethyl acralate (Blank 1) 15.95 6) Polyacrylonitrile (Blank 2) 14.43 69 67 20 44 26 53 25 50 10 10 80 20 36 0e320 320e700 700e950 0e375 375e680 0e346 346e700 Please cite this article in press as: B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and Devices (2017), http://dx.doi.org/10.1016/ j.jsamd.2017.07.004 B.S Surendra, M Veerabhadraswamy / Journal of Science: Advanced Materials and Devices xxx (2017) 1e7 and 2858 cmÀ1 and their bending vibrations at 1445 cmÀ1 and 1379 cmÀ1 in the CH3 group The stretching vibrations of carbonyl (C]O) group appeared at 1727 cmÀ1 and their bending vibration showed at 1151, 1094 and 1023 cmÀ1 The methylacrylate-HMF showed the bands at 2957 and 2920 cmÀ1 for CeH stretching, 1728 cmÀ1 for C]O stretching, 1436 cmÀ1 for CH3 bending, the peaks at 1236, 1183, 1149, 1112 and 1075 cmÀ1 for CeO bending vibrations [30] All the polymer compounds showed the band at ~3351 cmÀ1 confirming the presence of free hydroxyl group except blank polymers due to the absence of free hydroxyl group Comparison of these polymers with blank polymers showed the formation of HMF polymer of different monomers Conclusion In summary, we demonstrated a two-step insitu reaction for the conversion of most abundant renewable raw material non edible seed cakes into valuable chemical intermediate and polymer products in a simple, quick and economical method The production of the HMF intermediate from the deoiled seed cakes is a worldwide strategy towards the reduction of use of chemicals for the organic synthesis HMF is one of the top value added chemical intermediates and plays a vital role in insitu synthesis of polymer products using acid modified clays under microwave heating The prepared heterogeneous catalyst can be used as an efficient acid mediated catalyst, which is easily separated from the reaction products and thus considered as one 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intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and Devices (2017), http://dx.doi.org/10.1016/ j.jsamd.2017.07.004 ... B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and... B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and... B.S Surendra, M Veerabhadraswamy, Microwave assisted synthesis of polymer via bioplatform chemical intermediate derived from Jatropha deoiled seed cake, Journal of Science: Advanced Materials and