Unlike polyolefin synthesis, where catalysts can be used to control the microstructure and generate multiple different materials from a single monomer, polyester microstructures are typically dictated by the monomer feedstock structure. Here, catalyst control of the degree of branching in poly(dodeceyloate) via hydroesterificative polymerization of 10-undecen-1-ol is reported. By varying palladium precursors and monophosphine ligands, poly(dodecyloate) with α methyl branching percentages ranging from 28 to 78% can be achieved. These polyesters initially feature moderate molecular weights ranging from 7.2 to 9.4 kg/mol, but an additional transesterification step can increase the molecular weight up to 15.8 kg/mol, sidestepping challenges associated with low conversions in branch-selective hydroesterification reactions. The branched content can be further fine-tuned through a dual catalytic strategy, where the use of phosphine ligand mixtures can yield multiple active catalytic species (of varying regioselectivity) that can cooperatively construct the polyester through step-growth polymerization.

中文翻译：

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10-十一碳烯-1-醇加氢酯化聚合中聚酯支化的催化剂控制

与聚烯烃合成不同，聚烯烃合成可以使用催化剂来控制微观结构并从单一单体生成多种不同的材料，而聚酯微观结构通常由单体原料结构决定。在此，报道了通过 10-十一碳烯-1-醇的加氢酯化聚合来控制聚（十二碳酸酯）的支化度。通过改变钯前体和单膦配体，可以获得α甲基支化百分比在28%至78%范围内的聚十二烷酸酯。这些聚酯最初具有 7.2 至 9.4 kg/mol 的中等分子量，但额外的酯交换步骤可以将分子量提高至 15.8 kg/mol，从而回避了支链选择性加氢酯化反应中低转化率相关的挑战。支链含量可以通过双催化策略进一步微调，其中使用膦配体混合物可以产生多种活性催化物质（具有不同的区域选择性），这些物质可以通过逐步增长聚合协同构建聚酯。