Stability of star-shaped RAFT polystyrenes under mechanical and thermal stress

Altintas, O., Abbasi, M., Riazi, K., Goldmann, A. S., Dingenouts, N., Wilhelm, M., & Barner-Kowollik, C. (2014) Stability of star-shaped RAFT polystyrenes under mechanical and thermal stress. Polymer Chemistry, 5(17).

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Abstract

Well-defined three-arm and four-arm star polymers designed via a Z-group approach carrying trithiocarbonate functionalities at the core are prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization featuring molecular weights of Mn,SEC = 156 kDa, D = 1.16 (3-arm) and M n,SEC = 162 kDa, D = 1.15 (4-arm) based on multi-angle laser light scattering (MALLS) detection, respectively. The star-shaped polystyrenes are subjected (in bulk) to thermal stress in the temperature range between 140 and 200 °C from 10 minutes up to 96 h. The thermally treated 3-arm and 4-arm star polymers are analyzed via size exclusion chromatography (SEC) to quantify the degradation process at variable temperatures as a function of time under an argon atmosphere. Cleavage rate coefficients of the star polymers are deduced as a function of temperature, resulting in activation parameters for the cleavage process, i.e. Ea = 131 kJ mol-1; A = 3.93 × 10 11 s-1 (Mn,SEC = 156 kDa, D = 1.16, 3-arm star) and Ea, = 134 kJ mol-1; A = 9.13 × 1011 s-1 (Mn,SEC = 162 kDa, D = 1.15, 4-arm star), respectively. Processing of the star-shaped polymers is mimicked via a small scale counter rotating twin screw extrusion to achieve nonlinear shear and elongation flow under pressure. Furthermore, a rheological assessment via the linear shear deformation region (small amplitude oscillatory shear, SAOS) allows for a correlation of the processing conditions with the thermal degradation properties of the star polymers in the melt. Zero shear viscosity (η0) as a criterion of the degradation process is measured in the rheometer and correlated to the weight-average molecular weight, Mw. This journal is © the Partner Organisations 2014.

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ID Code: 99374
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :5
Export Date: 5 September 2016
Correspondence Address: Wilhelm, M.; Polymeric Materials, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr, 76128 Karlsruhe, Germany; email: manfred.wilhelm@kit.edu
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Keywords: Extrusion, Molecular weight, Polystyrenes, Shear flow, Activation parameter, Multiangle laser light scattering, Processing condition, Reversible addition-fragmentation chain transfer polymerization, Thermal degradation properties, Variable temperature, Weight-average molecular weight, Zero shear viscosity, Thermal stress
DOI: 10.1039/c4py00484a
ISSN: 17599954
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 27 Sep 2016 01:12

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