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

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52 B. Charleux, R. Faust 3.3.1.1.6 Poly(isobutylene) p-Poly(isobutylene)styrene (S-PIB) was synthesized by polymerizing IB with the p-(b-bromoethyl)cumyl chloride (34) /(CH 3 ) 3 Al initiating system in CH 3 Cl at –55 °C, followed by dehydrobromination with tert-BuOK [84]. The polymerization proceeded in the absence of chain transfer to monomer. Although termination was operational with (CH 3 ) 3 Al, it was apparently slower than propagation since the MWs could be adjusted in the 4000–34,000 g mol –1 range by changing the [monomer]/[initiator] ratio. Close to complete monomer conversions could be obtained with [monomer]/[initiator]
Synthesis of Branched Polymers by Cationic Polymerization 53 ester functionality was retained after quenching the ester-Lewis acid complexes. (35) Following quantitative methylation of the w-tert-chloro site by trimethyl aluminum, the methylated polyisobutylene methacrylate macromonomer was copolymerized with MMA by Group Transfer Polymerization [87]. PMMA-g-PIB graft copolymers with controlled MW and composition were obtained. The structure and physical properties were determined by the [MMA]/[MA-PIB] and [MMA]/[Initiator] ratios. 3.3.1.2 Synthesis Using a Functional Capping Agent In this method, the polymerizable group is incorporated at the w-end of the macromonomer by a reaction between a functionalized capping agent and the living end of the polymer. To obtain well-defined macromonomers with one polymerizable end group per chain, controlled MW and narrow MWD, the following criteria should be fulfilled: - living polymerization conditions; - quantitative coupling of the quencher to the polymer end; - formation of a stable bond; - absence of side reaction of the functional group during the quenching process. 3.3.1.2.1 Poly(vinyl ethers) Sodium salt of malonate carbanions are known to react quantitatively with the living ends of poly(vinyl ether)s to give a stable carbon-carbon bond [45]. This reaction was performed to end-functionalize living poly(vinyl ether)s with a vinyl ether polymerizable end group using the functional malonate ion 36 [73, 89]. (36) IBVE was polymerized with the HI/I 2 initiating system in CH 2Cl 2 at –15 °C. After complete consumption of the monomer, five equivalents of the quenching agent (with respect to the living end) were added. An instantaneous reaction was evidenced by the precipitation of sodium iodide. Poly(IBVE) with controlled MW (by the monomer to HI molar ratio) and narrow MWD was obtained as ev-
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142 Advances in Polymer Science Edi
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Branched Polymers I Volume Editor:
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Volume Editor Dr. Jacques Roovers I
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Preface While books have been writt
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Contents Synthesis of Branched Poly
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Poly(macromonomers): Homo- and Copo
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Poly(macromonomers), Homo- and Copo
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Dendrimers and Dendrimer-Polymer Hy
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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 101-142 233 Ka
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Author Index Volumes 101-142 235 Og
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Author Index Volumes 101-142 237 Su
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Subject Index Addition-fragmentatio
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Subject Index 241 Microphases 11z,
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