Abstract
Despite abundant researches on petroleum based polymer nanocomposites over micro and macro composites, these nanocomposites suffer from deprived biodegradability, highly inherent flammability and less mechanical strength. The present work describes the preparation of a biodegradable nanocomposite based on carboxymethyl cellulose-g-polyacrylonitrile (CMC-g-PAN) and montmorillonite (MMT) nanoclay by using ammonium persulfate (APS) as an initiator, methylene bis-acrylamide (MBA) as a crosslinker via emulsifier free emulsion polymerisation. The formation of the nanocomposites was confirmed by Fourier transform infrared (FTIR), X-ray diffraction (XRD) and Transmission electron microscope (TEM) analysis. The formation of CMC-g-PAN copolymer was confirmed by means of proton nuclear magnetic resonance (1H NMR) spectra. The improvement in thermal stability of the nanocomposites over copolymer was outstanding. More importantly, incorporating MMT enables the nanocomposite to achieve a dramatically reduced peak heat release rate of 536 ± 03 kW m−2 shown in cone calorimetry tests and higher limiting oxygen index (LOI) value indicating improved fire retardancy. In addition, the tensile strength of the nanocomposite was also increased by around 41% with 5% w/v MMT contents. This is explained on the basis of strong interfacial adhesion between CMC and MMT through PAN. Meanwhile for its better commercialization, the eco-friendly nature was studied via biodegradation.
Similar content being viewed by others
References
Ghasemlou M, Khodaiyan F, Oromiehie A, Yarmand MS (2011) Development and characterisation of a new biodegradable edible film made from kefiran, an exopolysaccharide obtained from kefir grains. Food Chem 127:1496–1502
Sahoo PK, Samal R, Swain SK, Rana PK (2008) Synthesis of poly (butyl acrylate)/sodium silicate nanocomposite fire retardant. Euro Polym J 44:3522–3528
Cheng S, Zhang Y, Cha R, Yang J, Jiang X (2016) Water-soluble nanocrystalline cellulose films with highly transparent and oxygen barrier properties. Nanoscale 8:973–978
Okamo M, John B (2013) Synthetic biopolymer nanocomposites for tissue engineering scaffolds. Prog Polym Sci 38:1487–1503
Saurabh CK, Gupta S, Bahadur J, Mazumder S, Variyar PS, Sharma A (2013) Radiation dose dependent change in physiochemical, mechanical and barrier properties of guar gum based films. Carbohydr Polym 98:1610–1617
Cervin NT, Andersson L, Ng JBS, Olin P, Bergstrom L, Wagberg L (2013) Lightweight and strong cellulose materials made from aqueous foams stabilized by nanofibrillated cellulose. Biomacromolecules 14:503–511
Chang C, Duan B, Cai J, Zhang L (2010) Superabsorbent hydrogels based on cellulose for smart swelling and controllable delivery. Eur Polym J 46:92–100
Wang Q, Guo J, Xu D, Cai J, Qiu Y, Ren J, Zhang L (2015) Facile construction of cellulose/montmorillonite nanocomposite biobased plastics with flame retardant and gas barrier properties. Cellulose 22:3799–3810
Zhao J, Zhang X, Tu R, Lu C, He X, Zhang W (2014) Mechanically robust, flame-retardant and anti-bacterial nanocomposite films comprised of cellulose nanofibrils and magnesium hydroxide nanoplatelets in a regenerated cellulose matrix. Cellulose 21:1859–1872
Gupta KC, Sahoo S, Khandekar K (2002) Graft copolymerization of ethyl acrylate onto cellulose using ceric ammonium nitrate as initiator in aqueous medium. Biomacromolecules 3:1087–1094
Takacs E, Wojnarovits L, Borsa J, Racz I (2010) Hydrophilic/hydrophobic character of grafted cellulose. Radiat Phys Chem 79:467–470
Mukherjee A, Halder S, Datta D, Anupam K, Hazra B, Mandal MK, Halder G (2017) Free radical induced grafting of acrylonitrile on pre-treated rice straw for enhancing its durability and flame retardancy. J Adv Res 8:173–183
Boruah M, Gogoi P, Manhar AK, Khannam M, Mandal M, Dolui SK (2014) Biocompatible carboxymethylcellulose-g-poly(acrylic acid)/OMMT nanocomposite hydrogel for in vitro release of vitamin B12. RSC Adv 4:43865–43873
Bao Y, Ma J, Li N (2011) Synthesis and swelling behaviors of sodium carboxymethyl cellulose-g-poly(AA-co-AM-co-AMPS)/MMT superabsorbent hydrogel. Carbohydr Polym 84:76–82
Yang XH, Zhu WL (2007) Viscosity properties of sodium carboxymethyl cellulose solutions. Cellulose 14:409–417
Taghizadeh MT, Sabouri N (2013) Biodegradation behaviors and water adsorption of poly(vinyl alcohol)/starch/carboxymethyl cellulose/clay nanocomposites. Int Nano Letters 3:51–58
Farag S, Al-Afaleq EI (2002) Preparation and characterization of saponified delignified cellulose polyacrylonitrile-graft copolymer. Carbohydr Polym 48:1–5
Pourjavadi A, Zohuriaan-Mehr MJ (2002) Modification of carbohydrate polymers via grafting in air. 2. Ceric-initiated graft copolymerization of acrylonitrile onto natural and modified polysaccharides. Starch 54:482–488
Morgan AB (2006) Flame retarded polymer layered silicate nanocomposites: a review of commercial and open literature systems. Polym Adv Technol 17:206–217
Samal B, Rana PK, Sahoo PK (2008) Preparation and characterization of biodegradable Waterabsorbent PAN/SS nanocomposite. Polym Compos 29:1203–1209
Strawhecker KE, Manias E (2000) Structure and properties of poly(vinyl alcohol)/Na+ montmorillonite nanocomposites. Chem Mater 12:2943–2949
Jena DK, Sahoo PK (2018) Development of biodegradable cellulose-g-poly(butyl acrylate)/kaolin nanocomposite with improved fire retardancy and mechanical properties. J Appl Polym Sci 135:45968–45975
Lin JJ, Cheng IJ, Wang R, Lee RJ (2001) Tailoring basal Spacings of montmorillonite by poly(oxyalkylene)diamine intercalation. Macromolecules 34:8832–8834
Wang L, Xie X, Su S, Feng J, Wilkie CA (2010) A comparison of the fire retardancy of poly (methyl methacrylate) using montmorillonite, layered double hydroxide and kaolinite. Polym Degrad Stab 95:572–578
Alekseeva OV, Rodionova AN, Bagrovskaya NA, Agafonov AV, Noskov AV (2017) Effect of the Organobentonite filler on structure and properties of composites based on hydroxyethyl cellulose. J Chem 2017:1603937, 11 pages. https://doi.org/10.1155/2017/1603937
Chou CC, Lin JJ (2005) One-step exfoliation of montmorillonite via phase inversion of amphiphilic copolymer emulsion. Macromolecules 38:230–233
Choi YS, Wang KH, Xu M, Chung IJ (2002) Synthesis of exfoliated Polyacrylonitrile/Na−MMT nanocomposites via emulsion polymerization. Chem Mater 14:2936–2939
Stretz HA, Wootan MW, Cassidy PE, Koo JH (2005) Effect of exfoliation on poly(styrene-co-acrylonitrile)/montmorillonite nanocomposite flammability. Polym Adv Technol 16:239–248
Shami Z, Sharifi-Sanjani N (2010) The role of na-montmorillonite on thermal characteristics and morphology of electrospun pan nanofibers. Fibers Polym 11:695–699
Zahedi Y, Fathi-Achachlouei B, Yousefi AR (2018) Physical and mechanical properties of hybrid montmorillonite/zinc oxide reinforced carboxymethyl cellulose nanocomposites. Int J Biol Macromol 108:863–873
Qiu H, Yu J (2008) Polyacrylate/(carboxymethylcellulose modified montmorillonite) superabsorbent nanocomposite: preparation and water absorbency. J Appl Polym Sci 107:118–123
Samal B, Sahoo PK (2007) Nonconventional emulsion polymerization of acrylonitrile catalyzed by in situ metal complex. Chin J Polym Sci 25:145–152
Sahoo PK, Bhattacharjee SP, Samal RK (1985) Influence of cu(II)/salicylaldehyde couple on potassium monopersulphate decomposition and acrylonitrile polymerization in solution. Euro Polym J 21:499–503
Samal R, Sahoo PK (2010) Synthesis of a biodegradable polyacrylonitrile/sodium silicate nanocomposite fire retardant. Ind J. Chem Tech 17:139–144
Vermani OP, Narula AK (1989) Applied Chemistry (Theory and Practical) Wiley Eastern Ltd, New Delhi, India, 36
Wang Z, Ning A, Xie P, Gao G, Xie L, Li X, Song A (2017) Synthesis and swelling behaviors of carboxymethyl cellulose-based superabsorbent resin hybridized with graphene oxide. Carbohydr Polym 157:48–56
Jena DK, Sahoo PK (2018) Simultaneous improvement of mechanical and fire retardant properties of synthesised biodegradable guar gum-g-poly(butyl acrylate)/montmorillonite nanocomposite. Polym Degrad Stab 154:37–45
Patil AS, Gadad AP, Hiremath RD, Joshi SD (2018) Biocompatible tumor micro-environment responsive CS-g-PNIPAAm co-polymeric nanoparticles for targeted Oxaliplatin delivery. J Polym Res 25:77–89
Ho FFL, Klosiewict DW (1980) Proton nuclear magnetic resonance spectrometry for determination of substituents and their distribution in Carboxymethylcellulose. Anal Chem 52:913–916
Minagawa M, Ute K, Kitayama T, Hatada K (1994) Determination of Stereoregularity of γ-Irradiation Canal polymerized Polyacrylonitrile by 1H 2D J-resolved NMR spectroscopy. Macromolecules 27:3669–3671
Grassie N, Torrence BJD, Fortune JD, Gemmel JD (1965) Reactivity ratios for the copolymerization of acrylates and methacrylates by nuclear magnetic resonance spectroscopy. Polymer 6:653–658
Pitchumani S, Reddy CR, Rajadurai S (1982) Reactivity ratios of ethyl acrylate, n-butyl methacrylate copolymer system by 1H-NMR. J Polym Sci, Polym Chem Ed 20:277–282
Chiu CW, Huang TK, Wang YC, Alamani BG, Lin JJ (2014) Intercalation strategies in clay/polymer hybrids. Prog Polym Sci 39:443–485
Uthirakumar P, Nahm KS, Hahn YB, Lee YS (2004) Preparation of polystyrene/montmorillonite nanocomposites using a new radical initiator-montmorillonite hybrid via in situ intercalative polymerization. Eur Polym J 40:2437–2444
Yin H, Chen H, Chen D (2010) Morphology and mechanical properties of polyacrylonitrile/ attapulgite nanocomposite. J Mater Sci 45:2372–2380
Gilman JW, Kashiwagi T (2000) Polymer-Clay Nanocomposites edited by T J Pinnavaia & G W Beall (John Wiley & Sons: New York), 193
Samal R, Sahoo PK (2009) Development of a biodegradable rice straw-g-poly(methyl methacrylate)/sodium silicate composite flame retardant. J Appl Polym Sci 113:3710–3715
Lucas N, Bienaime C, Belloy C, Queneudec M, Silvestre F, Nava-Saucedo J-E (2008) Polymer biodegradation: mechanisms and estimation techniques - a review. Chemosphere 73:429–442
Acknowledgements
This work was financially supported by UGC-BSR fellowship, Govt, of India to DKJ (SRF) [F.No.25-1/2014-15(BSR)/7-175/2007/(BSR)].
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no conflict of interest.
Rights and permissions
About this article
Cite this article
Sahoo, P.K., Jena, D.K. Synthesis and study of mechanical and fire retardant properties of (carboxymethyl cellulose -g-polyacrylonitrile)/montmorillonite biodegradable nanocomposite. J Polym Res 25, 260 (2018). https://doi.org/10.1007/s10965-018-1659-3
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10965-018-1659-3