Soluble Head-to-Tail Regioregular Polythiazoles: Preparation, Properties, and Evidence for Chain-Growth Behavior in the Synthesis via Kumada-Coupling Polycondensation
Soluble Head-to-Tail Regioregular Polythiazoles: Preparation, Properties, and Evidence for Chain-Growth Behavior in the Synthesis via Kumada-Coupling Polycondensation
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可溶性头尾立体规整聚噻唑：制备、性质以及 Kumada 偶联缩聚合成中链增长行为的证据
作者：
F. Pammer;J. Jäger;B. Rudolf;Y. Sun
通过“反向”单体的Kumada偶联缩聚反应，合成了侧链上含有硅醚的头尾区域规整聚(4-烷基噻唑)S。研究了它们的光学性质、电化学性质和体相性质，提出了聚合过程中存在准活性链状生长行为的证据。合成了两种分别含有三异丙基硅基和二异丁基十八烷基硅基的聚合物PTzTIP和PTzDIBO。PTzTIP基本上不溶于水，而PTzDIBO完全溶于包括正己烷在内的常见有机溶剂，在CHCl3中通过凝胶渗透色谱(GPC)测定，PTzTIP的数均相对分子质量超过100 kDa，对应的平均聚合度超过200。通过与山本聚合合成的头到头相连的联苯并噻唑(PBTzTIP)的比较，证实了规则的头尾结构的形成。区域规则的PTzDIBO可以通过不同的聚合方案获得，包括两个新的芳基镍配合物的外部引发，这两个新的芳基镍配合物提供了特别低的多分散性(<；1.4atMn>；100 kDa)。此外，在一系列间歇聚合实验中观察到了所获得的分子量与单体/催化剂比之间的直接关系，这与链增长缩聚过程一致。通过与模型化合物的比较，可以证明预催化剂-芳基部分进入了聚合物链中。官能化端基可通过~1H核磁共振独立测定其相对分子质量，与凝胶渗透色谱测得的结果吻合较好，进一步证实了链生长的发生。
Head-to-tail regioregular poly(4-alkylthiazole)s containing silylethers in the side-chains were synthesized via Kumada-Coupling polycondensation of “reversed” monomers, that were metalated at the sterically hindered 5-position. Their optical, electrochemical, and bulk properties have been studied, and evidence is presented that indicates the occurrence of quasi-living chain-growth behavior in the polymerization process. Two polymers,PTzTIPandPTzDIBO, featuring triisopropylsilyl and diisobutyloctadecylsilyl side chains, respectively, were prepared.PTzTIPis largely insoluble, whilePTzDIBOis fully soluble in common organic solvents, including hexane, and readily gave number-averaged molecular weights exceeding 100 kDa, corresponding to an average degree of polymerization greater than 200, as determined via gel-permeation chromatography (GPC) in CHCl3. The formation of a regular head-to-tail regiostructure could be confirmed through comparison with a head-to-head–tail-to-tail regioregular polybithiazole (PBTzTIP), synthesized via Yamamoto-polymerization of a head-to-head-linked bithiazole. RegioregularPTzDIBOcould be obtained via different polymerization protocols, including external initiation with two new aryl-nickel-complexes, which furnished material with particularly low polydispersities (<1.4 atMn> 100 kDa). Furthermore, a direct correlation between the obtained molecular weight and the monomer/catalyst ratio was observed in series of batch polymerization experiments, in agreement with a chain-growth polycondensation process. The incorporation of the precatalyst–aryl moiety into the polymer chains could be proven by comparison with a model compound. The functionalized end-groups allowed to independently determine the molecular weight via1H NMR, which gave good agreement with the values obtained from GPC, further corroborating the occurrence of chain-growth.
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DOI：
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发表时间：
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DOI：
10.1002/pola.26449
发表时间：
2013
期刊：
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作者：
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