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Synthesis of polystyrene modified with fluorine atoms: Monomer reactivity ratios and thermal behavior
Author(s) -
Wiacek Malgorzata,
Jurczyk Sebastian,
Kurcok Malgorzata,
Janeczek Henryk,
SchabBalcerzak Ewa
Publication year - 2014
Publication title -
polymer engineering and science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.503
H-Index - 111
eISSN - 1548-2634
pISSN - 0032-3888
DOI - 10.1002/pen.23627
Subject(s) - comonomer , azobisisobutyronitrile , differential scanning calorimetry , activation energy , thermal stability , polymer chemistry , polystyrene , materials science , thermogravimetric analysis , glass transition , styrene , radical polymerization , reactivity (psychology) , copolymer , polymerization , monomer , thermal decomposition , analytical chemistry (journal) , polymer , chemistry , organic chemistry , thermodynamics , composite material , pathology , medicine , physics , alternative medicine
Homo‐ and copolymers of 4‐fluorostyrene (FSt) and styrene (St) were synthesized with different feed ratios using free radical bulk polymerization with azobisisobutyronitrile (AIBN) as initiator. It yielded series of (co)polymers with various amounts of included FSt, P(St‐ co ‐FSt) (5–50 mol%) and PFSt. The effect of the initiator concentration on the molecular weights of the homopolymers, that is, PSt and PFSt was investigated. Copolymer compositions were determined by nuclear magnetic resonance spectroscopy. The relative reactivity ratios of both comonomers were determined by applying the conventional linearization methods of Jaacks (J), Finemann–Ross (F–R), inverted Finemann–Ross (IF–R), and Kelen‐Tüdos (K–T). The reactivity ratios values of St and FSt obtained from J plot are 1.06 and 0.84, F–R plot are 1.18 and 1.06, IF–R 1.01 and 0.86, and K–T plot 1.04 and 0.88, respectively. Thermal properties of prepared (co)polymers, that is, glass transition temperature ( T g ) and thermal stability, were determined from differential scanning calorimetry and thermogravimetrical measurements. The lack of significant influence of FSt comonomer content on T g of (co)polymers was observed. Additionally, the thermal degradation kinetics of obtained PSt and PFSt was studied by thermogravimetric analysis. Kinetic parameters such as the thermal decomposition activation energy ( E ) and frequency factor ( A ) were estimated by Ozawa model [ E ( O ) and A ( O ), respectively] and Kissinger model [ E ( K ) and A ( K ), respectively]. The activation energy and the frequency factor of PFSt (253 kJ/mol) were higher than PSt (236 kJ/mol). The resulting activation energies estimated using the two methods were quite close. POLYM. ENG. SCI., 54:1170–1181, 2014. © 2013 Society of Plastics Engineers