Sains Malaysiana 42(4)(2013): 509–514
Reactivity
Ratio Determination of Newly Synthesized Copolymers from Glycidyl Methacrylate
and Tetrahydrofurfuryl Acrylate
(Penentuan Nisbah Kereaktifan Kopolimer Baru yang Disintesis
daripada Glisidil Metakrilat dan Tetrahidrofurfuril Akrilat)
Ahmad Danial Azzahari, Rosiyah Yahya*
& Aziz Hassan
Department of Chemistry, University of Malaya, 50603 Kuala
Lumpur, Malaysia
Diserahkan: 23 Jun 2011 / Diterima: 23 Mac 2012
ABSTRACT
Copolymers from different feed compositions of glycidyl
methacrylate (GMA) and tetrahydrofurfuryl acrylate (THFA)
were synthesized using free radical polymerization in toluene solution at
70±1°C using benzoyl peroxide (BPO) as initiator. The polymers
were characterized by 1H NMR,13C NMR and DEPT spectroscopic
techniques. The copolymer compositions were determined using 1H NMR analysis.
Reactivity ratios for GMA and THFA were
determined by the Kelen-Tudos, Tidwell-Mortimer and error-in-variables model
methods. The results showed that all these copolymerizations were strictly
linear systems describable by the Mayo-Lewis equation based on the terminal
model and that accurate reactivity ratio data can be obtained.
Keywords: Copolymerization; glycidyl methacrylate; reactivity
ratios; tetrahydrofurfuryl acrylate
ABSTRAK
Kopolimer daripada komposisi glisidil metakrilat
(GMA)
dan tetrahidrofurfuril akrilat (THFA) telah disintesis dengan
menggunakan pempolimeran radikal bebas dalam larutan toluena pada 70±1°C
menggunakan benzoyl peroksida (BPO) sebagai pemula. Kopolimer ini dicirikan oleh teknik
spektroskopi1H NMR, 13C NMR dan DEPT.
Nisbah kereaktifan untuk GMA dan THFA telah
ditentukan oleh kaedah Kelen-Tudos, Tidwell-Mortimer dan model
ralat-dalam-pemboleh ubah. Keputusan menunjukkan bahawa semua
kopolimerisasi ini merupakan sistem linear yang boleh diterangkan oleh
persamaan Mayo-Lewis berdasarkan model terminal dan data nisbah kereaktifan
yang tepat boleh diperoleh.
Kata kunci: Glisidil metakrilat; kopolimerisasi;
nisbah kereaktifan; tetrahidrofurfuril akrilat
RUJUKAN
Adhikari, B. & Majumdar, S. 2004. Polymers
in sensor applications. Progress in Polymer Science 29(7):
699-766.
ArIca, M.Y., Bayramog lu, G. &
Biçak, N. 2004. Characterisation of tyrosinase immobilised onto spacer-arm attached
glycidyl methacrylate-based reactive microbeads. Process Biochemistry 39(12):
2007-2017.
Bakhshi, H., Zohuriaan-Mehr, M.J., Bouhendi, H. &
Kabiri, K. 2009. Spectral and chemical determination of
copolymer composition of poly (butyl acrylate-co-glycidyl methacrylate) from
emulsion polymerization. Polymer Testing 28(7):
730-736.
Bayramoglu, G., Akgöl, S., Bulut, A.,
Denizli, A. & ArIca, M.Y. 2003. Covalent
immobilisation of invertase onto a reactive film composed of 2-hydroxyethyl
methacrylate and glycidyl methacrylate: Properties and application in a
continuous flow system. Biochemical Engineering Journal 14(2): 117-126.
Box, G.E.P. 1958. Problemes dexperimentation. Bulletin de l’Institut
international de statistique 36: 215.
Box, G.E.P., Hunter, W.G. & Hunter,
J.S. 1978. Statistics for
Experiments. New York: John Wiley & Sons.
Espinosa, M.H., del Toro, P.J.O. & Silva, D.Z. 2001.
Microstructural analysis of poly(glycidyl
methacrylate) by 1Hand 13C NMR spectroscopy. Polymer 42(8): 3393-3397.
Fineman, M. & Ross, S.D. 1950. Linear
method for determining monomer reactivity ratios in copolymerization. Journal
of Polymer Science 5(2): 259-262.
Ghi, P.Y., Hill, D.J.T. &
Whittaker, A.K. 1999. A
study of the copolymerization of hydroxyethyl methacrylate and tetrahydrofurfuryl
methacrylate. Journal of Polymer Science Part A: Polymer Chemistry 37(19):
3730-3737.
Grassie, N., Torrance, B.J.D., Fortune,
J.D. & Gemmell, J.D. 1965. Reactivity ratios for the copolymerization of acrylates and
methacrylates by nuclear magnetic resonance spectroscopy. Polymer 6(12):
653-658.
Hall, C.E., Datta, D. & Hall,
E.A.H. 1996. Parameters which
influence the optimal immobilisation of oxidase type enzymes on methacrylate
copolymers as demonstrated for amperometric biosensors. Analytica Chimica
Acta 323(1-3): 87-96.
Kelen, T. & Tüdős, F. 1974. A new improved linear graphical method for determing
copolymerization reactivity ratios. Reaction Kinetics and Catalysis Letters 1(4):
487-492.
Kelen, T. & Tüdős, F. 1975. Analysis of the linear methods for
determining copolymerization reactivity ratios. I. A new improved linear
graphic method. Journal of Macromolecular Science: Part A - Chemistry 9(1):
1 - 27.
Malmsten, M. & Larsson, A. 2000. Immobilization of trypsin on porous glycidyl methacrylate
beads: Effects of polymer hydrophilization. Colloids and Surfaces B:
Biointerfaces 18(3-4): 277-284.
Mayo, F.R. & Lewis, F.M. 1944. Copolymerization. I. A
basis for comparing the behavior of monomers in copolymerization; the
copolymerization of styrene and methyl methacrylate. Journal of the American
Chemical Society 66(9): 1594-1601.
Nino, G.D., Turacchio, M., D’Archivio, A.A., Lora, S.,
Corain, B. & Antonini, G. 2004. Catalytic activity of bovine
lactoperoxidase supported on macroporous poly(2-hydroxyethyl
methacrylate-co-glycidyl methacrylate). Reactive and Functional Polymers 61(3):
411-419.
Odian, G.G. 2004. Principles of Polymerization. 4th ed. New Jersey:
Wiley-Interscience.
Pérez, J.P.H., López-Cabarcos, E. & López-Ruiz, B. 2006. The application of methacrylate-based polymers to enzyme
biosensors. Biomolecular Engineering 23(5): 233-245.
Rajendrakumar, K. & Dhamodharan, R. 2009. Ambient
temperature atom transfer radical copolymerization of tetrahydrofurfuryl
methacrylate and methyl methacrylate: Reactivity ratio determination. European
Polymer Journal 45(9): 2685-2694.
Reilly, P.M. & Patino-Leal, H.
1981. A Bayesian study of
the error-in-variables model. Technometrics 23(3): 221-231.
Reilly, P.M., Reilly, H.V. & Keeler, S.E. 1993.
Algorithm AS 286: Parameter estimation in the error-in-variables model. Journal of the Royal Statistical Society. Series C
(Applied Statistics) 42(4): 693-701.
Schaefer, J. 1969. Carbon-13 nuclear
magnetic resonance analysis of ethylene oxide-maleic anhydride copolymers. Macromolecules 2(2): 210-214.
Tidwell, P.W. & Mortimer, G.A. 1965. An
improved method of calculating copolymerization reactivity ratios. Journal
of Polymer Science Part A: General Papers3(1):
369-387.
Yang, W., Hu, J., Tao, Z., Li, L., Wang, C. & Fu, S.
1999. Dispersion copolymerization of styrene and glycidyl
methacrylate in polar solvents. Colloid and Polymer Science 277(5):
446-451.
*Pengarang
untuk surat-menyurat; email: rosiyah@um.edu.my
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