TY - JOUR
T1 - Determination of propagation rate coefficients for an α-substituted acrylic ester
T2 - Pulsed laser polymerization of dimethyl itaconate
AU - Yee, Lachlan H.
AU - Coote, Michelle L.
AU - Chaplin, Rodney P.
AU - Davis, Thomas P.
PY - 2000/6/15
Y1 - 2000/6/15
N2 - Pulsed laser polymerization experiments have been performed on the bulk polymerization of dimethyl itaconate over the temperature range 20-50°C. The activation energy and frequency factor were calculated as 24.9 kJ/mol-1 and 2.15 × 105 L/mol-1s-1, respectively. The activation energy is comparable with the methacrylate series of monomers. The frequency factor is relatively small and reflects steric hindrance in the transition state caused by the bulky 1,1, disubstitution in the monomer (and consequently the radical). The Mark-Houwink-Kuhn-Sakurada constants were also determined for poly(dimethyl itaconate) in tetrahydrofuran, these are reported as 46 × 10-5 dL/g (K) and 0.51 (α). The influence of penultimate units (γ-substituents) on homopropagation reactions is discussed particularly for polymerizations leading to significant 1,3 interactions in the resultant polymer.
AB - Pulsed laser polymerization experiments have been performed on the bulk polymerization of dimethyl itaconate over the temperature range 20-50°C. The activation energy and frequency factor were calculated as 24.9 kJ/mol-1 and 2.15 × 105 L/mol-1s-1, respectively. The activation energy is comparable with the methacrylate series of monomers. The frequency factor is relatively small and reflects steric hindrance in the transition state caused by the bulky 1,1, disubstitution in the monomer (and consequently the radical). The Mark-Houwink-Kuhn-Sakurada constants were also determined for poly(dimethyl itaconate) in tetrahydrofuran, these are reported as 46 × 10-5 dL/g (K) and 0.51 (α). The influence of penultimate units (γ-substituents) on homopropagation reactions is discussed particularly for polymerizations leading to significant 1,3 interactions in the resultant polymer.
UR - http://www.scopus.com/inward/record.url?scp=0033723397&partnerID=8YFLogxK
U2 - 10.1002/(SICI)1099-0518(20000615)38:12<2192::AID-POLA80>3.0.CO;2-G
DO - 10.1002/(SICI)1099-0518(20000615)38:12<2192::AID-POLA80>3.0.CO;2-G
M3 - Article
AN - SCOPUS:0033723397
SN - 0887-624X
VL - 38
SP - 2192
EP - 2200
JO - Journal of Polymer Science, Part A: Polymer Chemistry
JF - Journal of Polymer Science, Part A: Polymer Chemistry
IS - 12
ER -