Quantitative Synthesis of Star-Shaped Poly(vinyl ether)s with a Narrow Molecular Weight Distribution by Living Cationic Polymerization
Star-shaped poly(vinyl ether)s with narrow molecular weight distributions were obtained from polymer-linking reactions of living polymers with a divinyl compound based on living cationic polymerization. For example, living polymers (DP n = 50−300) of isobutyl vinyl ether (IBVE), prepared with a cati...
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| Published in | Journal of the American Chemical Society Vol. 128; no. 23; pp. 7497 - 7504 |
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| Main Authors | , , |
| Format | Journal Article |
| Language | English |
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Washington, DC
American Chemical Society
14.06.2006
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| Abstract | Star-shaped poly(vinyl ether)s with narrow molecular weight distributions were obtained from polymer-linking reactions of living polymers with a divinyl compound based on living cationic polymerization. For example, living polymers (DP n = 50−300) of isobutyl vinyl ether (IBVE), prepared with a cationogen/EtAlCl2 at 0 °C in hexane in the presence of ethyl acetate, were allowed to react with a small amount of 1,4-cyclohexanedimethanol divinyl ether (DVE-1) to give a star-shaped poly(IBVE) in quantitative yield (100%). In addition, a notable feature of this star-shaped polymer was extremely narrow molecular weight distribution (M w/M n = 1.1−1.2). The structure of divinyl compounds and reaction conditions for the linking reaction are key factors for achieving quantitative yield of star-shaped polymers. To our best knowledge, this is the first example of selective preparation of star-shaped polymers with narrow molecular weight distribution via one-pot polymer-linking reactions, which has never been achieved in any other mechanisms. The M w and the number of arms per molecule ranged from 6 × 104 to 30 × 104 and 9 to 44, respectively. Thermosensitive star polymers were also synthesized in quantitative yield, and the products were found to undergo sensitive phase separation and physical gelation. |
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| AbstractList | Star-shaped poly(vinyl ether)s with narrow molecular weight distributions were obtained from polymer-linking reactions of living polymers with a divinyl compound based on living cationic polymerization. For example, living polymers (DP(n) = 50-300) of isobutyl vinyl ether (IBVE), prepared with a cationogen/EtAlCl(2) at 0 degrees C in hexane in the presence of ethyl acetate, were allowed to react with a small amount of 1,4-cyclohexanedimethanol divinyl ether (DVE-1) to give a star-shaped poly(IBVE) in quantitative yield (100%). In addition, a notable feature of this star-shaped polymer was extremely narrow molecular weight distribution (M(w)/M(n) = 1.1-1.2). The structure of divinyl compounds and reaction conditions for the linking reaction are key factors for achieving quantitative yield of star-shaped polymers. To our best knowledge, this is the first example of selective preparation of star-shaped polymers with narrow molecular weight distribution via one-pot polymer-linking reactions, which has never been achieved in any other mechanisms. The M(w) and the number of arms per molecule ranged from 6 x 10(4) to 30 x 10(4) and 9 to 44, respectively. Thermosensitive star polymers were also synthesized in quantitative yield, and the products were found to undergo sensitive phase separation and physical gelation. Star-shaped poly(vinyl ether)s with narrow molecular weight distributions were obtained from polymer-linking reactions of living polymers with a divinyl compound based on living cationic polymerization. For example, living polymers (DP n = 50−300) of isobutyl vinyl ether (IBVE), prepared with a cationogen/EtAlCl2 at 0 °C in hexane in the presence of ethyl acetate, were allowed to react with a small amount of 1,4-cyclohexanedimethanol divinyl ether (DVE-1) to give a star-shaped poly(IBVE) in quantitative yield (100%). In addition, a notable feature of this star-shaped polymer was extremely narrow molecular weight distribution (M w/M n = 1.1−1.2). The structure of divinyl compounds and reaction conditions for the linking reaction are key factors for achieving quantitative yield of star-shaped polymers. To our best knowledge, this is the first example of selective preparation of star-shaped polymers with narrow molecular weight distribution via one-pot polymer-linking reactions, which has never been achieved in any other mechanisms. The M w and the number of arms per molecule ranged from 6 × 104 to 30 × 104 and 9 to 44, respectively. Thermosensitive star polymers were also synthesized in quantitative yield, and the products were found to undergo sensitive phase separation and physical gelation. |
| Author | Shibata, Takaho Kanaoka, Shokyoku Aoshima, Sadahito |
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| Keywords | Thermal properties Atomic force microscopy Molecular weight distribution Molecular weight determination Optical properties Living polymer Star polymer Cationic polymerization Isobutyl vinyl ether polymer Polymer structure Gel permeation chromatography |
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| Snippet | Star-shaped poly(vinyl ether)s with narrow molecular weight distributions were obtained from polymer-linking reactions of living polymers with a divinyl... |
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| SubjectTerms | Applied sciences Exact sciences and technology Organic polymers Physicochemistry of polymers Polymerization Preparation, kinetics, thermodynamics, mechanism and catalysts |
| Title | Quantitative Synthesis of Star-Shaped Poly(vinyl ether)s with a Narrow Molecular Weight Distribution by Living Cationic Polymerization |
| URI | http://dx.doi.org/10.1021/ja057611h https://api.istex.fr/ark:/67375/TPS-SVHJHD0T-7/fulltext.pdf https://www.ncbi.nlm.nih.gov/pubmed/16756304 https://search.proquest.com/docview/68046746 |
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