In this study, we demonstrated that the Suzuki–Miyaura catalyst transfer polycondensation (SCTP) of the triolborate-type fluorene monomer, viz. potassium 2-(7-bromo-9,9-dihexyl-9H-fluorene-2-yl)triolborate, can be an efficient and versatile approach to the precise synthesis of poly[2,7-(9,9-dihexylfluorene)]s (PFs) and PF-containing block and graft copolymers. SCTP of the triolborate-type monomer proceeded rapidly in a THF/H₂O mixed solvent at −10 °C using an iodobenzene derivative/Pd₂(dba)₃·CHCl₃/t-Bu₃P initiating system. Kinetic and post-polymerization experiments revealed that SCTP proceeded via the chain-growth and living polymerization mechanisms. The most important feature of the present polymerization system is that only a small amount of base and water can sufficiently promote the reaction. The well-controlled nature of this polymerization system enabled the synthesis of high-molecular-weight PFs (M_n = 5–69 kg mol⁻¹) with narrow dispersity (Đ_M = 1.14–1.38) and α-end-functionalized PFs. Most importantly, PF-containing block and graft copolymers were successfully synthesized, beginning with various iodobenzene-functionalized macroinitiators; this was difficult to achieve by the conventional SCTP of pinacolboronate-type fluorene monomer. One of the key factors for the successful block and graft copolymer syntheses is the reduced water content in the polymerization medium, which suppressed the potential precipitation/aggregation of the macroinitiators.

中文翻译：

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Suzuki–Miyaura的三硼酸酯型芴单体的催化剂转移缩聚反应：可通过各种大分子引发剂快速进入含聚芴的嵌段和接枝共聚物

在这项研究中，我们证明了triolborate型芴单体，的铃木-宫浦催化剂转移缩聚（SCTP）即。2-（7-溴-9,9-二己基-9 H-芴-2-基）三硼硼酸钾可能是精确合成聚[2,7-（9,9-二己基芴）的有效方法] s（PFs）和含PF的嵌段和接枝共聚物。使用碘代苯衍生物/ Pd ₂（dba）₃ ·CHCl ₃ / t -Bu ₃ P引发体系，在-10°C的THF / H ₂ O混合溶剂中，三硼酸酯型单体的SCTP快速进行。动力学和后聚合实验表明，SCTP通过链增长和活性聚合机制。本聚合体系的最重要的特征是仅少量的碱和水可以充分促进反应。此聚合体系的良好控制的性质启用高分子量的PF的合成（中号_Ñ = 5-69公斤摩尔^-1）与窄分散度（Đ_中号= 1.14–1.38）和α端官能化的PF。最重要的是，从各种碘苯官能化的大分子引发剂开始，成功地合成了含PF的嵌段和接枝共聚物。传统的频哪醇硼酸酯型芴单体的SCTP很难做到这一点。成功的嵌段和接枝共聚物合成的关键因素之一是聚合介质中水含量的降低，这抑制了大分子引发剂的潜在沉淀/聚集。