论文部分内容阅读
π-二芳烃铬(0)能催化齐聚全氟丙烯,得到两种两聚体(ⅡA和ⅡB),两种三聚体(ⅢA和ⅢB)和两种脱氟三聚体(ⅣA和ⅣB)。后者系由ⅢB先氢化,而后脱除HF而形成的。脱除下来的氟化氢加成到全氟丙烯上形成2-氢代七氟丙烷。同位素标记证明了氢化ⅢB的氢来自催化剂的配位体,可能经过π-σ重排。本文提出了可能的机理。π-二苯铬(0)能催化聚合全氟丁炔-2,得到白色粉末状的聚全氟丁炔-2;能催化共聚全氟丙烯和全氟丁炔-2,得到固体和蜡状的共聚物。用分子内Wittig反应成功地合成了R_fC≡C-CN(R_f=CF_3,C_2F_5,C_3F_7),继而用π-二苯铬(0)催化聚合C_2F_5C≡C-CN,得到了黑色的粉末状产物。
The π-diaryl chromium (0) can catalyze the oligomerization of perfluoropropene to give two dimers (IIA and IIB), two trimers (IIIA and IIIB) and two defluoro trimers (IVA and IVB). The latter is formed by the first hydrogenation of IIB and then the removal of HF. The removed hydrogen fluoride is added to perfluoropropene to form 2-hydroheptaheptafluoropropane. Isotopic labeling proves that hydrogenation of hydrogenated IIIB comes from the ligand of the catalyst and may undergo π-σ rearrangement. This article suggests possible mechanisms. π-diphenyl chromium (0) can catalyze the polymerization of perfluorobutyne-2, to obtain a white powder of polyperfluorobutyn-2; can catalyze the copolymerization of perfluoropropylene and perfluorobutyn-2, to obtain a solid and waxy Copolymer. The intramolecular Wittig reaction was successfully used to synthesize R_fC≡C-CN (R_f = CF_3, C_2F_5, C_3F_7), and then the C_2F_5C≡C-CN was catalyzed by π-diphenyl chromium (0) to obtain the black powdery product.