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Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers
The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η(5)-cyclopentadienyl)dimethyl zirconium (Cp(2)ZrMe(2)) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C(6)F(5))(4)](–)[Me(2)NHPh](+), as...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6780830/ https://www.ncbi.nlm.nih.gov/pubmed/31527533 http://dx.doi.org/10.3390/polym11091510 |
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author | Zouganelis, Stavros Choinopoulos, Ioannis Goulas, Ioannis Pitsikalis, Marinos |
author_facet | Zouganelis, Stavros Choinopoulos, Ioannis Goulas, Ioannis Pitsikalis, Marinos |
author_sort | Zouganelis, Stavros |
collection | PubMed |
description | The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η(5)-cyclopentadienyl)dimethyl zirconium (Cp(2)ZrMe(2)) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C(6)F(5))(4)](–)[Me(2)NHPh](+), as an initiation system. The reactivity ratios are calculated using both linear graphical and non-linear methods. Structural parameters of the copolymers are obtained by calculating the dyad sequence fractions and the mean sequence length, which are derived using the monomer reactivity ratios. The glass transition temperatures (T(g)) of the copolymers are measured by Differential Scanning Calorimetry (DSC), and the results are compared with predictions based on several theoretical models. The statistical copolymers are further employed as scaffolds for the synthesis of graft copolymers having poly(vinyl ether)s as a backbone and either poly(ε-caprolactone) (PCL) or poly(l-lactide) (PLLA) as side chains. Both the grafting “onto” and the grafting “from” methodologies are employed. The reaction sequence is monitored by Size Exclusion Chromatography (SEC), NMR and IR spectroscopies. The advantages and limitations of each approach are thoroughly examined. |
format | Online Article Text |
id | pubmed-6780830 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-67808302019-10-30 Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers Zouganelis, Stavros Choinopoulos, Ioannis Goulas, Ioannis Pitsikalis, Marinos Polymers (Basel) Article The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η(5)-cyclopentadienyl)dimethyl zirconium (Cp(2)ZrMe(2)) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C(6)F(5))(4)](–)[Me(2)NHPh](+), as an initiation system. The reactivity ratios are calculated using both linear graphical and non-linear methods. Structural parameters of the copolymers are obtained by calculating the dyad sequence fractions and the mean sequence length, which are derived using the monomer reactivity ratios. The glass transition temperatures (T(g)) of the copolymers are measured by Differential Scanning Calorimetry (DSC), and the results are compared with predictions based on several theoretical models. The statistical copolymers are further employed as scaffolds for the synthesis of graft copolymers having poly(vinyl ether)s as a backbone and either poly(ε-caprolactone) (PCL) or poly(l-lactide) (PLLA) as side chains. Both the grafting “onto” and the grafting “from” methodologies are employed. The reaction sequence is monitored by Size Exclusion Chromatography (SEC), NMR and IR spectroscopies. The advantages and limitations of each approach are thoroughly examined. MDPI 2019-09-16 /pmc/articles/PMC6780830/ /pubmed/31527533 http://dx.doi.org/10.3390/polym11091510 Text en © 2019 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 Zouganelis, Stavros Choinopoulos, Ioannis Goulas, Ioannis Pitsikalis, Marinos Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers |
title | Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers |
title_full | Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers |
title_fullStr | Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers |
title_full_unstemmed | Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers |
title_short | Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers |
title_sort | statistical copolymers of n-butyl vinyl ether and 2-chloroethyl vinyl ether via metallocene-mediated cationic polymerization. a scaffold for the synthesis of graft copolymers |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6780830/ https://www.ncbi.nlm.nih.gov/pubmed/31527533 http://dx.doi.org/10.3390/polym11091510 |
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