Patent GB-769498-A (GB)
Title: Organosilicon amines
IPC: C07F7/10
Filed: 1954-12-08
Abstract: The invention comprises amino-organosilanes and siloxanes prepared therefrom, the silanes having the formula (Y2NR)R1bSiX3-b, where Y is an alkyl or trihydrocarboxylsilyl radical, X is Cl, Br of H, R is a divalent saturated aliphatic or cycloaliphatic hydrocarbon radical containing at least 3 carbon atoms, the amino group being attached to a carbon atom at least 3 carbon atoms away from the Si, R1 is a monovalent hydrocarbon or halogenated hydrocarbon radical free from aliphatic unsaturation, and b is 0 or 1.  The silanes are prepared by reacting a mixture of a silane of the formula R1bSiX4-b, where at least one X is H, with an amine containing one unsaturated aliphatic radical containing at least 3 carbon atoms or one unsaturated cycloaliphatic radical, containing only one C=C linkage which linkage is at least between the second and third carbon atom removed from the N atom, at least one of the remaining two substituents on the amine being alkyl or trihydrocarbonyl radicals.  The reaction is preferably effected at temperatures of 50 DEG  to 150 DEG  C. in the presence of a catalyst such as benzoyl peroxide or tert. butyl perbenzoate. Suitable unsaturated amines are allyl, undecenyl, allylmethyl, octadecenyl, allylstearyl and allyldimethyl amines and those of the formula <FORM:0769498/IV(a)/1> and <FORM:0769498/IV(a)/2> The siloxanes have the general unit formula <FORM:0769498/IV(a)/3> where R11 is an alkyl radical or hydrogen atom, and are prepared by hydrolysis of the above silanes, preferably in the presence of an inert solvent such as ether, benzene or toluene. They may be copolymerized with other siloxanes and may be reacted with polyfunctional organic compounds, e.g. with dicarboxylic acids to give polyamide resins useful for coatings or for making fibres, or with other functional siloxanes, such as those described in Specifications 769,496 and 769,497.  The siloxanes, per se, are useful as surface-active agents.  In the examples: (1) N,N-bis-(trimethylsilyl) - 3 - phenylsilylpropyl amine is obtained from N,N-bis-(trimethylsilyl) allyl amine and monophenylsilane, and is hydrolysed to the siloxane of unit formula <FORM:0769498/IV(a)/4> (2) the compound BrSi(CH2)3NM33 is obtaine from dimethyl allyl amine and tribromosilane and is hydrolysed to Me2N(CH2)3SiO1,5; (3) N-trimethylsilyl undecenyl amine is prepared from undecenyl amine and hexamethyldisilazane and is reacted with phenylsilane to give C6H5SiH2C11H22 NHSiMe3. Hydrolysis with dilute HCl in dioxane gives the silanol of unit formula (OH)2Si(C6H5) C11H22NH2 which is heated with KOH to give the siloxane; (4) the compound <FORM:0769498/IV(a)/5> is obtained from methyldibromosilane and the silylamine <FORM:0769498/IV(a)/6> and is hydrolysed to the siloxane <FORM:0769498/IV(a)/7> (5) the compound <FORM:0769498/IV(a)/8> is obtained from the silyl amine <FORM:0769498/IV(a)/9> and chlorophenyl silane, and is hydrolysed to the siloxane <FORM:0769498/IV(a)/100> (6) the silane MeSiBr2(CH2)3N (SiMe3)2 is obtained from N,N-bis-(trimethylsilyl) allyl amine and methyl dibromosilane, and is hydrolysed to <FORM:0769498/IV(a)/111> (7) equimolecular amounts of the silane (Me3 Si)2N(CH2)3Si(Me)Br2, phenylmethyl dichlorosilane and trimethylchlorosilane were cohydrolysed giving a copolymeric siloxane having the unit formul  H2N(CH2)3Si(Me)O, C6H5(Me)SiO and Me3SiO0,5. The aminopropyl silane was likewise cohydrolysed with phenyltrichlorosilane, chlorophenyltrichlorosilane and methylvinyldichlorosilane.