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(1)二甲基二氯硅烷和甲基三氯硅烷的部分醇解,产物的收率很高,达到97.7—98.9%。用分馏方法可以确定各步产物的成分,因此可以应用 Fuoss 方程式计算这两种氯硅烷逐步竞争醇解的反应速度常数比。在下列反应中(CH_6)_2SiCl_2+C_2H_5OH(?)(CH_6)_2Si(OC_2H_5)Cl+HCl(CH_6)_2Si(OC_2H_5)Cl+C_2H_5OH(?)(CH_6)_2Si(OC_2H_5)_2+HClCH_(?)SiCl(?)+C_2H_5OH(?)CH_(?)Si(OC_2H_5)Cl_2+HClCH_(?)Si(OC_2H_5)Cl_2+C_2H_5OH(?)CH_6Si(OC_2H_5)_2Cl+HClCH_(?)Si(OC_2H_5)_2Cl+C_2H_5OH(?)CH_6Si(OC_2H_5)_6+HCl求得 K_1:K_2=17:2;K_3:K_4:K_5=60:27:2。(2)以二甲基乙氧基氯硅烷和甲基二乙氧基硅烷进行相互竞争醇解,求得 K_2:K_(?)=1∶4.6。另以三甲基氯硅烷和二甲基乙氧基氯硅烷进行相互竞争醇解,(CH(?))(?)SiCl+C_2H_5OH(?)(CH_(?))(?)SiOC_2H_5+HCl求得 K_6:K(?)=1:7。 (3)整理上列结果,得到三种不同官能度的甲基氯硅烷的逐步竞争和相互竞争醇解反应速度常数比为:K_1∶K_2∶K_3∶K_4∶K_5∶K_6=60∶7∶960∶430∶32∶1可以看出在甲基氯硅烷分子中,甲基或乙氧基数目增加,均使氯原子的醇解速度降低,而甲基的影响较乙氧基为大。
(1) The partial alcoholysis of dimethyldichlorosilane and methyltrichlorosilane yields a high yield of 97.7-98.9%. Fractionation can be used to determine the composition of products in each step. Therefore, the Fuoss equation can be used to calculate the reaction rate constant ratio of the two chlorosilanes competing for alcoholysis step by step. (CH_6) _2Si (OC_2H_5) Cl + HCl (CH_6) _2Si (OC_2H_5) Cl + C_2H_5OH () (CH_6) _2Si (OC_2H_5) _2 + HClCH_ () SiCl (CH_6) _2SiCl_2 + (?) + C_2H_5OH (?) CH_ (?) Si (OC_2H_5) Cl_2 + HClCH _ (?) Si (OC_2H_5) Cl_2 + C_2H_5OH (?) CH_6Si (OC_2H_5) _2Cl + HClCH _ (?) Si (OC_2H_5) _2Cl + C_2H_5OH ?) CH_6Si (OC_2H_5) _6 + HCl K_1: K_2 = 17: 2; K_3: K_4: K_5 = 60: 27: 2. (2) K 2: K _ (?) = 1: 4.6 was obtained by competitive alcohololysis with dimethylethoxychlorosilane and methyldiethoxysilane. In addition, trimethylchlorosilane and dimethylethoxychlorosilane were used to compete with each other for alcoholysis. (CH (?))? SiCl + C 2 H 5 SO? (CH? K_6: K (?) = 1: 7. (3) After finishing the above results, the stepwise competition and mutual competition of methylchlorosilanes with three different functionalities were obtained: K_1: K_2: K_3: K_4: K_5: K_6 = 60: 7: 960 : 430: 32: 1 It can be seen in the methylchlorosilane molecules, methyl or ethoxy number increased, both the alcoholysis rate of chlorine atoms decreased, while the impact of methyl than ethoxy.