Sains Malaysiana 46(3)(2017): 485–491

http://dx.doi.org/10.17576/jsm-2017-4603-17

 

Epoxidation and Hydroxylation of Liquid Natural Rubber

(Pengepoksidaan dan Penghidroksilan Getah Asli Cecair)

 

NUR HANIS ADILA AZHAR¹, HAMIZAH MD RASID¹ & SITI FAIRUS M. YUSOFF^1,2*

 

¹School of Chemical Sciences and Food Technology, Faculty of Science and Technology

Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor Darul Ehsan, Malaysia

 

²Polymer Research Center (PORCE), Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor Darul Ehsan, Malaysia

 

Diserahkan: 24 Jun 2016/Diterima: 15 Ogos 2016

 

ABSTRACT

Liquid natural rubber (LNR) was functionalized into liquid epoxidized natural rubber (LENR) and hydroxylated LNR (LNR-OH) via oxidation using a Na₂WO₄/CH₃COOH/H₂O₂ catalytic system. Microstructures of LNR and functionalized LNRs were characterized using Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopies. The effect of CH₃COOH, H₂O₂ Na₂WO₄, reaction time and temperature on epoxy content were investigated. LNR-OH was obtained when oxidation reaction was conducted at a longer reaction time, higher temperature or excess amount of catalyst. Thermogravimetric analysis (TGA) reported the thermal behavior of functionalized LNRs. Molecular weight and polydispersity index (PDI) were determined using gel permeation chromatography (GPC).

 

Keywords: Diols; epoxidation; hydroxylated; liquid natural rubber; oxidation

 

ABSTRAK

Getah asli cecair (LNR) telah diperfungsikan kepada getah asli cecair terepoksida (LENR) dan getah asli cecair terhidroksil (LNR-OH) melalui tindak balas pengoksidaan menggunakan sistem pemangkinan Na₂WO₄/CH₃COOH/H₂O₂. Mikrostruktur LNR dan LNR diperfungsi dicirikan menggunakan spektroskopi Fourier transformasi inframerah (FTIR) dan resonans magnet nukleus (NMR). Kesan CH₃COOH, H₂O₂, Na₂WO₄, masa dan suhu tindak balas ke atas kandungan epoksi dikaji. LNR-OH diperoleh apabila tindak balas pengoksidaan dijalankan pada masa yang lebih panjang, suhu yang lebih tinggi atau lebihan amaun pemangkin. Analisis termogravimetri (TGA) melaporkan sifat terma LNR yang terfungsi. Berat molekul dan indeks kepoliserakan (PDI) ditentukan melalui kromatografi penelapan gel (GPC).

 

Kata kunci: Diol; getah asli cecair; pengepoksidaan; pengoksidaan; terhidroksil

RUJUKAN

Asaletha, R., Kumaran, M.G. & Thomas, S. 1998. Thermal behavior of natural rubber/polystyrene blends: Thermogravimetric and differential scanning calorimetric analysis. Polymer Degradation and Stability 61(3): 431-439.

Baker, C.S.L. & Gelling, I.R. 1987. Epoxidized natural rubber. In Development of Rubber Technology - 4, edited by Whelan, A. & Lee, K.S. London: Elsevier Applied Science. pp. 87-117.

Brosse, J.C., Campistron, I., Derouet, D., Hamdaoui, A.E., Houdayer, S., Reyx, D. & Ritoit-Gillier, S. 2000. Chemical modifications of polydiene elastomers: A survey and some recent results. Journal of Applied Polymer Science 78(8): 1461-1477.

Cai, Y., Li, S.D., Li, C.P., Li, P.W., Wang, C., Lv, M.Z. & Xu, K. 2007. Thermal degradations of chlorinated natural rubber from latex and chlorinated natural rubber from solution. Journal of Applied Polymer Science 106(2): 743-748.

Claramma, N.M., Nair, N.R. & Mathew, N.M. 1991. Production of liquid natural rubber by thermal depolymerization. Indian Journal of Natural Rubber Research 4: 1-7.

Dobre, T., Parvulescu, O.C., Sanchez-Marcano, J., Stoica, A., Stroescu, M. & Iavorschi, G. 2011. Characterization of gas permeation through stretched polyisoprene membranes. Separation and Purification Technology 82(1): 202-209.

Fieser, L.F. & Fieser, M. 1967. In Reagents for Organic Synthesis. New York: Wiley. p. 773.

Gan, S.N. & Ziana Abdul Hamid. 1997. Partial conversion of epoxide groups to diols in epoxidized natural rubber. Polymer 38(8): 1953-1956.

Gelling, I.R. & Porter, M. 1988. Chemical modification of natural rubber. In Natural Rubber Science and Technology, edited by Roberts, A.D. Oxford: Oxford University Press. p. 359.

Hahn, S.F. 1992. An improved method for the diimide hydrogenation of butadiene and isoprene containing polymers. Journal of Polymer Science A: Polymer Chemistry 30(3): 397-408.

Hanafi Ismail, Arjulizan Rusli & Azura A. Rashid. 2005. Maleated natural rubber as a coupling agent for paper sludge filled natural rubber composites. Polymer Testing 24(7): 856-862.

Hussin Mohd Nor & Ebdon, J.R. 1998. Telechilic liquid natural rubber: A review. Progress in Polymer Science 23(2): 143- 177.

Ibrahim Abdullah. 1994. Liquid natural rubber: Preparation and application. In Progress in Pacific Polymer Science 3. Proceedings of the Third Pacific Polymer Conference, edited by Ghiggino, K.P. Verlag Berlin Heidelberg: Springer. pp. 351-365.

Kargarzadeh, H., Ishak Ahmad, Ibrahim Abdullah, Thomas, R., Dufresne, A., Thomas, S. & Aziz Hassan. 2015. Functionalized liquid natural rubber and liquid epoxidized natural rubber: A promising green toughening agent for polyester. Journal of Applied Polymer Science 132(3): 41292.

Li, C., Liu, Y., Zeng, Q.Y. & Ao, N.J. 2013. Preparation and antimicrobial activity of quaternary phosphonium modified epoxidized natural rubber. Materials Letters 93: 145-148.

Lodha, A., Kilbey, S.M., Ramamurthy, P.C. & Gregory, R.V. 2001. Effect of annealing on electrical conductivity and morphology of polyaniline films. Journal of Applied Polymer Science 82(14): 3602-3610.

Mohd Suzeren Jamil, Ishak Ahmad & Ibrahim Abdullah. 2006. Effects of rice husk filler on the mechanical and thermal properties of liquid natural rubber compatibilized high-density polyethylene/natural rubber blends. Journal of Polymer Research 13(4): 315-321.

Nair, N.R., Thomas, S. & Mathew, N.M. 1997. Liquid natural rubber as a viscosity modifier in nitrile rubber processing. Polymer International 42(3): 289-300.

Norman, R.O.C. & Coxon, J.M. 1993. Principle of Organic Synthesis. New York: Blackie Academic & Professional. pp. 587-620.

Nur Hanis Adila Azhar, Naharullah Jamaluddin, Hamizah Md Rasid, Muhammad Jefri Mohd Yusof & Siti Fairus M. Yusoff. 2015. Studies on hydrogenation of liquid natural rubber using diimide. International Journal of Polymer Science 243038: 1-6.

Puskas, J.E., Chiang, K. & Barkakty, B. 2014. Natural rubber (NR) biosynthesis: Perspectives from polymer chemistry. In Chemistry, Manufacture and Applications of Natural Rubber, edited by Kohjiya, S. & Ikeda, Y. Cambridge: Elsevier. pp. 30-67.

Okieimen, F.E., Pavithran, C. & Bakare, I.O. 2005. Epoxidation and hydroxylation of rubber seed oil: One-pot multi-step reactions. European Journal of Lipid Science and Technology 107(5): 330-336.

Riyajan, S.A., Liaw, D.J., Tanaka, Y. & Sakdapipanich, J.T. 2007. Cationic cyclization of purified natural rubber in latex form with a trimethylsilyl triflate as a novel catalyst. Journal of Applied Polymer Science 105(2): 664-672.

Rosniza Hamzah, Mohamad Abu Bakar, Melati Khairuddean, Mohammed, I.A. & Rohana Adnan. 2002. A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative using NMR spectroscopy techniques. Molecules 17(9): 10974-10993.

Suhawati Ibrahim, Rusli Daik & Ibrahim Abdullah. 2014. Functionalization of liquid natural rubber via oxidative degradation of natural rubber. Polymers 6(12): 2928-2941.

Soheilmoghaddam, M., Wahit, M.U. &Akos, N.I. 2013. Regenerated cellulose/epoxidized natural rubber blend film. Materials Letters 111: 221-224.

Wan Ahmad Kamil Mahmood & Mohammad Hossein Azarian. 2015. Thermal, surface, nanomechanical and electrical properties of epoxidized natural rubber (ENR-50)/ polyaniline composite films. Current Applied Physics 15(5): 599-607.

Wongthong, P., Nakason, C., Pan, Q., Rempel, G.L. & Kiatkamjornwong, S. 2013. Modification of deproteinized natural rubber via grafting polymerization with maleic anhydride. European Polymer Journal 49(12): 4035-4046.

Yoksan, R. 2008. Epoxidized natural rubber for adhesive applications. Kasetsart Journal (Natural Science) 42: 325- 332.

Yu, H., Zeng, Z., Lu G. & Wang, Q. 2008. Processing characteristics and thermal stabilities of gel and sol of epoxidized natural rubber. European Polymer Journal 44(2): 453-464.

Zhang, J., Zhou, Q., Jiang, X.H., Du, A.K., Zhao, T., Kasteren J.V. & Wang, Y.Z. 2010. Oxidation of natural rubber using a sodium tungstate/acetic acid/hydrogen peroxide catalytic system. Polymer Degradation and Stability 95(6): 1077- 1082.

 

 

*Pengarang untuk surat-menyurat; email: sitifairus@ukm.edu.my