Synthesis of Polypropellanes via Ring-Opening Polymerization or Coupling Reaction

[3.3.1]正庚烷衍生物1，3-脱氢金刚烷(1)和5-丁基-1，3-脱氢金刚烷(2)的阳离子开环聚合反应在0℃的CH2Cl2中进行，反应时间为6~42 h，其中1和2上的中心σ-键全部开环，得到新型聚(3.3.1)-脱氢金刚烷(1)和聚(1，3-金刚烷)S，产率较高。得到的具有柔性丁基取代基的聚(2)可溶于氯仿、四氢呋喃和1，2-二氯苯，聚合度大于30，而聚(1)难溶于常见有机溶剂。所有脂肪族聚(1)和聚(2)均表现出较高的热稳定性，其10%失重温度分别为421和486℃。

Cationic ring-opening polymerizations of [3.3.1]propellane derivatives, 1,3-dehydroadamantane (1)and 5-butyl-1,3-dehydroadamantane (2), were carried out with CF_3SO_3H in CH_2Cl_2 at 0℃ for 6-42 h. The central σ-bonds in 1 and 2 were exclusively opened to afford novel poly([3.3.1]propellane)s, poly(1,3-adamantane)s, in good to quantitative yields. The resulting poly(2)possessing flexible butyl substituent was soluble in chloroform, THF, and 1,2-dichlorobenzene, and the degree of polymerization was estimated to be greater than 30, while the poly(1)was hardly soluble in the common organic solvents. All aliphatic poly(1)and poly(2)showed high thermal stability, whose 10% weight loss temperatures were 421 and 486℃, respectively.