142 Advances in Polymer Science Editorial Board: A. Abe. A.-C ...

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32 B. Charleux, R. Faust The coupling efficiency also depended on the length of the polymeric chain, the shorter being the more efficient. Moreover, a chloride counteranion was preferred due to the high affinity of silicon to chlorine. A tri- and a tetrafunctional coupling agent respectively 24 and 25 [48], both completely soluble in organic solvents, were then designed in order to obtain high yield of coupling of living poly(IBVE). The electron-donating alkoxyphenyl group in the a position enhanced the reactivity of the double bond and the radially shaped structure with rigid phenyl spacers led to well-separated reactive functions suitable for minimizing the steric hindrance previously observed with the malonate derivatives. (24) (25) Short chains (DP n~10) of living poly(IBVE) with Cl – counter-anion were prepared with the HCl/ZnCl 2 initiating system in CH 2Cl 2 at –15 °C. The coupling reaction with 24 and 25 respectively was carried out by the addition of a solution of the coupling agent in CH 2Cl 2 at about 80% conversion of IBVE and the reaction mixture was stirred during 24 h at the same temperature. The concentration of the nucleophilic functions was similar to that of the chain ends. In both cases, SEC analysis of the final products showed the complete shift of the low MW peak
Synthesis of Branched Polymers by Cationic Polymerization 33 Scheme 5 corresponding to the linear chains towards higher MWs. The higher MW was obtained with the tetrafunctional coupling agent and MWDs remained narrow for both coupled products (M w /M n
Page 1 and 2: 142 Advances in Polymer Science Edi
Page 3 and 4: Branched Polymers I Volume Editor:
Page 5 and 6: Volume Editor Dr. Jacques Roovers I
Page 7 and 8: Preface While books have been writt
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Poly(macromonomers): Homo- and Copo
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Author Index Volumes 101-142 Author
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Author IndexVolumes 101-142 231 Dun
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Author Index Volumes 101-142 235 Og
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Subject Index Addition-fragmentatio
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Subject Index 241 Microphases 11z,
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