Organosiloxanes (1) of the general formula R.sup.1.sub.4-n Si(OSiR.sub.3).sub.n, in which R is the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical having from 1 to 18 carbon atom(s) per radical or a substituted monovalent hydrocarbon radical having from 1 to 18 carbon atom(s) per radical, R.sup.1 represents R or a chlorine atom, and n is 3 or 4, are prepared by reacting organodisiloxanes (2) of the general formula (R.sub.3 Si).sub.2 O, with chlorosilanes (3) of the general formula R.sub.4-n SiCl.sub.n, in which R and n are the same as above, in the presence of phosphonitrile chlorides (4) and cocatalysts (5), in which the cocatalysts (5) are used concomitantly with the phosphonitrile chlorides (4) and are selected from the group consisting of amides of the general formula X--C(O)--R.sup.2, in which R.sup.2 is the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical or a substituted monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical, and X reresents a radical of the formula R.sup.2.sub.2 N- or ##STR1## where R.sup.2 is the same as above, R.sup.3 represents a divalent hydrocarbon radical having from 5 to 7 carbon atoms per radical, urea or urea derivatives of the general formula X--C(O)--X, where X is the same as above and cyanuric acid.
通式为R.sup.1.sub.4-n Si(OSiR.sub.3).sub.n的有机
硅氧烷(1),其中R相同或不同,代表氢原子或每个基团具有1至18个碳原子的单价碳氢基团或每个基团具有1至18个碳原子的取代的单价碳氢基团,R.sup.1代表R或
氯原子,n为3或4,通过在
磷氮
氯化物(4)和共催化剂(5)的存在下,将通式为(R.sub.3 Si).sub.2 O的有机二
硅氧烷(2)与通式为R.sub.4-n SiCl.sub.n的
氯硅烷(3)反应制备而成。其中,共催化剂(5)与
磷氮
氯化物(4)同时使用,并从以下群组中选择:通式为X--C(O)--R.sup.2的酰胺,其中R.sup.2相同或不同,代表每个基团具有1至8个碳原子的单价碳氢基团或每个基团具有1至8个碳原子的取代的单价碳氢基团,X代表通式为R.sup.2.sub.2 N-或##STR1##的基团,其中R.sup.2与上述相同,R.sup.3代表每个基团具有5至7个碳原子的双价碳氢基团,或通式为X--C(O)--X的
脲或
脲衍
生物,其中X与上述相同,并且是
氰尿酸。