Synthesis of Novel Organoboron Polymers by Heloboration Polymerization.

有机硼聚合物有望成为一种新型的反应性聚合物。在这项研究中，我们探索了一种通过末端二炔与三溴化硼反应制备有机硼聚合物的新方法。我们称之为卤化聚合。作为一个典型的例子，1，7-辛二炔与三溴化硼的多加成反应生成了棕色固体的有机卤化硼。该聚合物易溶于氯仿、二氯甲烷等常见有机溶剂。用凝胶渗透色谱(GPC)测得聚合物的相对分子质量为5,200“，相对分子质量为15,500。聚合物的结构得到了~1H-，^&lt；11&gt；B-核磁共振、红外光谱和紫外光谱的支持。目前的卤代聚合反应。在这种卤代聚合中，可以用不同的二炔类化合物生成相应的聚(有机溴卤化物)。在聚合物沉淀成乙醇的过程中，观察到了B-溴与B-OET的取代反应。聚合物与二元醇或水反应形成凝胶。聚合物中的B-Br键与苯乙炔发生进一步的卤代反应。通过与四氢呋喃的反应生成4-溴-L丁醇，也证明了该聚合物作为聚刘易斯酸的特性。

Organoboron polymers are expected as a novel type of reactive polymers. In this study, we explored a novel methodology for the preparation of organoboron polymers by the reaction of terminal diyne with boron tribromide. We termed this haloboration polymerization.As a typical example, the polyaddition between 1, 7-octadiyne and boron tribromide produced the corresponding poly (organoboron halide) as a brown solid. This polymer was soluble in common organic solvents such as chloroform and dichloromethane. The molecular weight of the obtained polymer was measured by GPC, from which Mn and Mw were found to be 5, 200"and 15, 500, respectively. The structure of the polymer was supported by its ^1H-, ^<11>B-NMR, IR and UV spectra. The present haloboration polymerization. was proved to proceed by cis addition of B-Br to C*C. In this haloboration polymerization, various diynes can be used to produce the corresponding poly (organobron halide)s.During the precipitation of the polymer into ethanol, the replacing reaction of B-Br to B-OET was observed. The reaction of the polymer with diol or with H_2O caused gelation. The B-Br bond in the polymer was subjected to the further haloboration reaction with phenylacetylene. The characteristic property of the polymer as a poly (Lewis acid) was also demonstrated by the reaction with THF to produce 4-bromo-, l-butanol after hydrolysis.