八甲基环四硅氮烷与二苯基二氯硅烷的反应研究

将八甲基环四硅氮烷 (OMCT)与Ph₂SiCl₂在190～210℃反应,获得的产物以正己烷溶解,分离出1,3-二氯-1,1,3,3-四苯基二硅氮烷(DCTPS)(Ⅰ),并得到滤液(Ⅱ)。滤液(Ⅱ)经减压加热反应,得到馏出液(Ⅲ)及残留物。采用¹H-NMR、²⁹Si-NMR谱、场解吸质谱(FD)、色质联用质谱等,对上述残留物及滤液(Ⅱ)、馏出液(Ⅲ)的二乙胺氨基化产物进行表征,确定各组分的结构。研究发现,OMCT与Ph₂SiCl₂ 的反应相当复杂,DCTPS等化合物是由不同的硅氮键断裂方式及不同的—SiMe₂—/—SiPh₂—交换反应形成的 ;滤液(Ⅱ)中的化合物经减压加热反应,形成产率约为20.3%的六苯基环三硅氮烷(HPCT)及一定量的DCTPS、Ph₂SiCl₂ 、M_e2SiCl₂ 等。

Reaction of octamethylcyclotetrasilazane with dichlorodiphenylsilane

Reaction of octamethylcyclotetrasilazane with Ph₂SiCl₂ was carried out at temperature of 190～210℃, and the mixture product was dissolved by n-hexane. By filtrating, 1,3-dichloro-1,1,3,3-tetraphenyldisilazane(DCTPS)(Ⅰ) and filtrate(Ⅱ) were obtained. After distilling the solvent, filtrate(Ⅱ) was conducted a reaction at 260℃ under reduced pressure of 5065Pa, and a distilled mixture (Ⅲ) was collected and a residue mixture was remained. The components of the residue mixture as well as the aminolysis products of the distilled mixture(III), and filtrate(II) were characterized by ¹H-NMR, ²⁹Si-NMR spectrum and field desorption(FD) mass spectrum. From the results, it was found that the reaction of OMCT with Ph₂SiCl₂ was very complicated, and DCTPS and other compounds were formed through different breaking modes of Si—N bonds in OMCT and different exchange reactions of—Me₂Si— groups with —SiPh₂— groups. Further reaction of filtrate(II) formed 20.3% hexaphenylcyclotrisilazane(HPCT) and some amount of DCTPS, Ph₂SiCl₂, Me₂SiCl₂ and so on.