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RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients
Well-defined poly(tert-butyldimethylsilyl methacrylate)s (TBDMSMA) were prepared by the reversible addition-fragmentation chain transfer (RAFT) process using cyanoisopropyl dithiobenzoate (CPDB) as chain-transfer agents (CTA). The experimentally obtained molecular weight distributions are narrow and...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6414831/ https://www.ncbi.nlm.nih.gov/pubmed/30966259 http://dx.doi.org/10.3390/polym10020224 |
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author | Nguyen, Minh Ngoc Margaillan, André Pham, Quang Trung Bressy, Christine |
author_facet | Nguyen, Minh Ngoc Margaillan, André Pham, Quang Trung Bressy, Christine |
author_sort | Nguyen, Minh Ngoc |
collection | PubMed |
description | Well-defined poly(tert-butyldimethylsilyl methacrylate)s (TBDMSMA) were prepared by the reversible addition-fragmentation chain transfer (RAFT) process using cyanoisopropyl dithiobenzoate (CPDB) as chain-transfer agents (CTA). The experimentally obtained molecular weight distributions are narrow and shift linearly with monomer conversion. Propagation rate coefficients (k(p)) and termination rate coefficients (k(t)) for free radical polymerization of TBDMSMA have been determined for a range of temperature between 50 and 80 °C using the pulsed laser polymerization-size-exclusion chromatography (PLP-SEC) method and the kinetic method via steady-state rate measurement, respectively. The CPDB-mediated RAFT polymerization of TBDMSMA has been subjected to a combined experimental and PREDICI modeling study at 70 °C. The rate coefficient for the addition reaction to RAFT agent (k(β1), k(β2)) and to polymeric RAFT agent (k(β)) is estimated to be approximately 1.8 × 10(4) L·mol(−1)·s(−1) and for the fragmentation reaction of intermediate RAFT radicals in the pre-equilibrium (k(-β1), k(-β2)) and main equilibrium (k(-β)) is close to 2.0 × 10(−2) s(−1). The transfer rate coefficient (k(tr)) to cyanoisopropyl dithiobenzoate is found to be close to 9.0 × 10(3) L·mol(−1)·s(−1) and the chain-transfer constant (C(tr)) for CPDB-mediated RAFT polymerization of TBDMSMA is about 9.3. |
format | Online Article Text |
id | pubmed-6414831 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-64148312019-04-02 RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients Nguyen, Minh Ngoc Margaillan, André Pham, Quang Trung Bressy, Christine Polymers (Basel) Article Well-defined poly(tert-butyldimethylsilyl methacrylate)s (TBDMSMA) were prepared by the reversible addition-fragmentation chain transfer (RAFT) process using cyanoisopropyl dithiobenzoate (CPDB) as chain-transfer agents (CTA). The experimentally obtained molecular weight distributions are narrow and shift linearly with monomer conversion. Propagation rate coefficients (k(p)) and termination rate coefficients (k(t)) for free radical polymerization of TBDMSMA have been determined for a range of temperature between 50 and 80 °C using the pulsed laser polymerization-size-exclusion chromatography (PLP-SEC) method and the kinetic method via steady-state rate measurement, respectively. The CPDB-mediated RAFT polymerization of TBDMSMA has been subjected to a combined experimental and PREDICI modeling study at 70 °C. The rate coefficient for the addition reaction to RAFT agent (k(β1), k(β2)) and to polymeric RAFT agent (k(β)) is estimated to be approximately 1.8 × 10(4) L·mol(−1)·s(−1) and for the fragmentation reaction of intermediate RAFT radicals in the pre-equilibrium (k(-β1), k(-β2)) and main equilibrium (k(-β)) is close to 2.0 × 10(−2) s(−1). The transfer rate coefficient (k(tr)) to cyanoisopropyl dithiobenzoate is found to be close to 9.0 × 10(3) L·mol(−1)·s(−1) and the chain-transfer constant (C(tr)) for CPDB-mediated RAFT polymerization of TBDMSMA is about 9.3. MDPI 2018-02-24 /pmc/articles/PMC6414831/ /pubmed/30966259 http://dx.doi.org/10.3390/polym10020224 Text en © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Nguyen, Minh Ngoc Margaillan, André Pham, Quang Trung Bressy, Christine RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients |
title | RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients |
title_full | RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients |
title_fullStr | RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients |
title_full_unstemmed | RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients |
title_short | RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients |
title_sort | raft polymerization of tert-butyldimethylsilyl methacrylate: kinetic study and determination of rate coefficients |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6414831/ https://www.ncbi.nlm.nih.gov/pubmed/30966259 http://dx.doi.org/10.3390/polym10020224 |
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