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An evaluation of the impact of SG1 disproportionation and the addition of styrene in NMP of methyl methacrylate
Author(s) -
Fierens Stijn K.,
Van Steenberge Paul H. M.,
Vermeire Florence,
Reyniers MarieFrançoise,
Marin Guy B.,
D'hooge Dagmar R.
Publication year - 2018
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.16111
Subject(s) - comonomer , styrene , copolymer , disproportionation , methyl methacrylate , polymer chemistry , chemistry , dispersity , monomer , nitroxide mediated radical polymerization , radical polymerization , polymerization , mole fraction , arrhenius equation , organic chemistry , polymer , catalysis , activation energy
A kinetic modeling study is presented for batch nitroxide mediated polymerization (NMP) of methyl methacrylate (MMA; nitroxide: N‐tert‐butyl‐N‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] (SG1)). Arrhenius parameters for SG1 disproportionation (A = 1.4 10 7 L mol −1 s −1 ; E a = 23 kJ mol −1 ) are reported, based on homopolymerization data accounting for unavoidable temperature variations with increasing time, that is, nonisothermicity. For low targeted chain lengths (TCLs ≤ 300), this nonisothermicity is also relevant for NMP of MMA with a small amount of styrene. Parameter tuning to copolymerization data confirms a penultimate monomer unit effect for activation (s a2 = k a12 /k a22 =6.7; 363 K; 1: MMA; 2: styrene). To obtain, for a broad TCL range (up to 800), a dispersity well below 1.3 an initial styrene mass fraction of ca. 10% is required. An interpretation of the comonomer incorporation is performed by calculating the fractions of activation‐growth‐deactivation cycles with a given amount of monomer units and the copolymer composition distribution . © 2018 American Institute of Chemical Engineers AIChE J , 64: 2545–2559, 2018