Efficient synthesis of high molar mass, first- to fourth-generation distributed dendronized polymers by the macromonomer approach.
Efficient synthesis of high molar mass, first- to fourth-generation distributed dendronized polymers by the macromonomer approach.
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DOI：
10.1002/chem.200305142
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发表时间：
2003-12
期刊：
影响因子：
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通讯作者：
A. Zhang;Bin Zhang;Eva Wächtersbach;Manfred Schmidt;A. Schlüter
中科院分区：
文献类型：
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作者：
A. Zhang;Bin Zhang;Eva Wächtersbach;Manfred Schmidt;A. Schlüter
合成了一系列第一代到第四代(G1-G4)树枝状大分子单体5、7、10和12，并研究了它们在自由基条件下的聚合行为。这些条件是热诱导自由基聚合(TRP)和原子转移自由基聚合(ATRP)。将色氨酸应用于所有单体，得到了聚合物PG1-PG4，其摩尔质量范围从PG1的几百万到PG2和PG3的估计数十万，以及PG4的低聚体系。ATRP仅适用于G1和G2单体5和7。对单体5的动力学研究提供了其聚合以受控方式进行的证据。单体与引发剂的最大摩尔质量比分别为300：1(对于5)和100：1(对于7)，这对应于PG1和PG2的摩尔质量约为M(N)=100000(dp(Calcd)(Pg1)=200，dp(Calcd)(Pg2)=90)。多分散度在通常范围内(PDI=1.1-1.2)。在DMF中用凝胶渗透色谱(GPC)测定摩尔质量，并用光散射法测定PG1的绝对摩尔质量。
A homologous series of first- to fourth-generation (G1-G4) dendronized macromonomers, 5, 7, 10, and 12, was synthesized, and their polymerization behavior under radical conditions investigated. These conditions were thermally induced radical polymerization (TRP) and atom-transfer radical poymerization (ATRP). TRP was applied to all monomers and gave polymers PG1-PG4, whose molar masses range from several millions for PG1 to estimated several hundreds of thousands for PG2 and PG3, and to the oligomeric regime for PG4. ATRP was applied only to the G1 and G2 monomers 5 and 7. Kinetic studies on monomer 5 provide evidence that its polymerization proceeds in a controlled fashion. The highest monomer-to-initiator ratios which still gave monomodal molar mass distributions were 300:1 (for 5) and 100:1 (for 7), which correspond to achievable molar mass regime for PG1 and PG2 of approximately M(n)=100 000 (DP(calcd)(PG1)=200, DP(calcd)(PG2)=90). The polydispersities lie in the usual range (PDI=1.1-1.2). The molar masses were determined by GPC in DMF with calibration against absolute molar masses of PG1 determined by light scattering.