Detailed analysis of termination kinetics in radical polymerization

Polymer International - Tập 72 Số 10 - Trang 869-880 - 2023
Michael Buback1, Gregory T. Russell2
1Institut für Physikalische Chemie Georg‐August‐Universität Göttingen Germany
2School of Physical and Chemical Sciences, University of Canterbury, Christchurch, New Zealand

Tóm tắt

AbstractStudies into the termination step of radical polymerization have mostly been carried out via chain‐length‐averaged properties. With the advent of pulsed laser polymerization (PLP) induced by single pulses (SPs), the analysis of termination rate coefficients kt has significantly improved. In conjunction with highly time‐resolved near‐infrared (NIR) detection of monomer consumption, SP‐PLP‐NIR allows for the measurement of chain‐length‐averaged termination rate coefficients as a function of temperature, pressure and degree of monomer conversion. With the addition of a suitable reversible addition−fragmentation chain−transfer agent, this technique even allows for the determination of chain‐length‐dependent termination rate coefficients kti,i, where i refers to the chain length of two terminating radicals of identical size. The decay of kti,i with chain length is more pronounced at small radical size below a crossover chain length ic. At larger chain lengths, kti,i decreases to a weaker extent. Thus, the so‐called composite model is perfectly suited for representing kti,i behaviour across the entire chain‐length range. A further clear improvement of kti,i determination is provided by the SP‐PLP‐EPR method, which directly measures the type and concentration of radicals via microsecond time‐resolved electron paramagnetic resonance (EPR) spectroscopy. This EPR‐assisted technique is particularly valuable for polymerizations where secondary radicals undergo backbiting and thus two types of radicals, secondary and tertiary, are simultaneously present, as is the case with acrylic monomers. © 2023 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

Từ khóa


Tài liệu tham khảo

10.1016/j.progpolymsci.2009.07.002

10.1002/macp.1961.020470114

10.1021/ja00865a011

10.1038/150336a0

10.1002/macp.1948.020010301

10.1524/zpch.1956.8.5_6.290

10.1002/macp.1947.020010110

10.1002/pol.1977.170150203

10.1021/ma60055a009

10.1002/pol.1976.130141107

10.1002/pol.1979.170170622

10.1002/masy.19870100105

10.1002/pol.1988.140260704

10.1002/pola.1992.080300516

10.1016/j.progpolymsci.2005.02.001

10.1002/macp.200290041

10.1002/marc.200400050

10.1002/mren.200900066

10.1021/acs.macromol.5b02660

10.1002/mats.200390029

10.1002/marc.1985.030061112

10.1021/ma00002a040

10.1021/ma00148a048

10.1021/ma801732r

10.1021/ma00170a024

10.1002/masy.200750201

10.1002/macp.1986.021870720

10.1071/CH02114

10.1002/0471440264.pst176

10.1021/ma00170a025

10.1002/(SICI)1521-3919(19980901)7:5<501::AID-MATS501>3.0.CO;2-U

10.1021/ma9908550

10.1021/ma00073a030

10.1021/ma060646x

10.1021/ma00135a021

10.1002/macp.1994.021950620

10.1021/ma971748d

10.1021/ma0350922

10.1021/ma970288l

10.1002/marc.200500067

10.1021/ma802078g

10.1002/masy.201300091

Kattner H, 2016, Dissertation

10.1524/zpch.219.3.295.59185

10.1002/marc.1986.030070505

10.1021/ma9814806

10.1021/ie9901933

10.1071/CH02074

10.1016/S0079-6700(01)00049-1

10.1021/ma7028902

10.1016/j.eurpolymj.2005.09.022

10.1002/macp.1995.021961016

10.1039/D2PY00147K

10.1002/macp.200600254

10.1002/macp.1990.021910710

10.1002/macp.1994.021950212

10.1071/CH07236

10.1021/jp054606r

10.1002/marc.200900335

10.1021/ma102278n

10.1021/acs.macromol.7b00745

Soerensen N, 2015, Dissertation

10.1021/ma1006039

10.1002/macp.201000781

10.1021/acs.macromol.7b02241

10.1002/marc.200350025

10.1002/macp.201700579

10.1021/ar00137a007

10.1021/acs.macromol.5b01921

10.1021/ma5022665

10.1002/marc.201100228

10.1002/macp.201300304

10.1002/macp.201500191

10.1016/0014-3057(90)90205-I

10.1021/acs.macromol.6b00483

10.1021/ma00069a011

10.1021/ma980169l

Thông tin
Thông tin xuất bản

Polymer International

Tập 72 Số 10

869-880

Thông tin tác giả