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Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts
Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes, such as hexamethylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, and 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, using water...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5914541/ https://www.ncbi.nlm.nih.gov/pubmed/29732072 http://dx.doi.org/10.1039/c7sc04234e |
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author | Fuchise, Keita Igarashi, Masayasu Sato, Kazuhiko Shimada, Shigeru |
author_facet | Fuchise, Keita Igarashi, Masayasu Sato, Kazuhiko Shimada, Shigeru |
author_sort | Fuchise, Keita |
collection | PubMed |
description | Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes, such as hexamethylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, and 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, using water as an initiator and strong organic bases, such as amidines, guanidines, phosphazene bases, and proazaphosphatrane, as catalysts produced a variety of polysiloxanes with controlled number-average molecular weights (M(n) = 2.64–102.3 kg mol(–1)), narrow polydispersity (Đ = 1.03–1.16), and well-defined symmetric structures. Controlled syntheses of statistical copolymers and triblock copolymers were achieved by copolymerizations of two cyclotrisiloxanes. Various terminal functionalities were successfully introduced by the end-capping reaction of propagating polysiloxanes using functional chlorosilanes. Kinetic investigations demonstrated that the polymerization proceeded through the initiator/chain-end activation mechanism, namely activations of water in the initiation reaction and of terminal silanols in propagating polysiloxanes in the propagation reaction. Catalytic activities of strong organic bases were revealed to depend on their Brønsted basicity and efficiency of the proton transfer in the initiation and propagation reactions. Guanidines possessing an R–N[double bond, length as m-dash]C(N)–NH–R′ unit, in particular 1,3-trimethylene-2-propylguanidine, showed excellent performance as a catalyst. In this system, even non-dehydrated solvents are usable for the polymerization. |
format | Online Article Text |
id | pubmed-5914541 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-59145412018-05-04 Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts Fuchise, Keita Igarashi, Masayasu Sato, Kazuhiko Shimada, Shigeru Chem Sci Chemistry Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes, such as hexamethylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, and 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, using water as an initiator and strong organic bases, such as amidines, guanidines, phosphazene bases, and proazaphosphatrane, as catalysts produced a variety of polysiloxanes with controlled number-average molecular weights (M(n) = 2.64–102.3 kg mol(–1)), narrow polydispersity (Đ = 1.03–1.16), and well-defined symmetric structures. Controlled syntheses of statistical copolymers and triblock copolymers were achieved by copolymerizations of two cyclotrisiloxanes. Various terminal functionalities were successfully introduced by the end-capping reaction of propagating polysiloxanes using functional chlorosilanes. Kinetic investigations demonstrated that the polymerization proceeded through the initiator/chain-end activation mechanism, namely activations of water in the initiation reaction and of terminal silanols in propagating polysiloxanes in the propagation reaction. Catalytic activities of strong organic bases were revealed to depend on their Brønsted basicity and efficiency of the proton transfer in the initiation and propagation reactions. Guanidines possessing an R–N[double bond, length as m-dash]C(N)–NH–R′ unit, in particular 1,3-trimethylene-2-propylguanidine, showed excellent performance as a catalyst. In this system, even non-dehydrated solvents are usable for the polymerization. Royal Society of Chemistry 2018-02-19 /pmc/articles/PMC5914541/ /pubmed/29732072 http://dx.doi.org/10.1039/c7sc04234e Text en This journal is © The Royal Society of Chemistry 2018 https://creativecommons.org/licenses/by-nc/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Fuchise, Keita Igarashi, Masayasu Sato, Kazuhiko Shimada, Shigeru Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts |
title | Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts
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title_full | Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts
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title_fullStr | Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts
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title_full_unstemmed | Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts
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title_short | Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts
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title_sort | organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5914541/ https://www.ncbi.nlm.nih.gov/pubmed/29732072 http://dx.doi.org/10.1039/c7sc04234e |
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