Patent GB-971233-A (GB)
Title: Improvements in or relating to nitrogen-containing organosilicon compounds
IPC: C08G77/00
Filed: 1962-09-26
Abstract: The invention comprises spirane compounds of general formula <FORM:0971233/C3/1> and also polysiloxanes and copolymeric siloxanes thereof, where R is a monovalent hydrocarbon radical or a monovalent hydrocarbon radical containing an ether linkage, a aminoalkyl-, aminophenyl-, halogenophenyl radical or an organosilyl radical (XR1)y2Siwhere each y is a monovalent + hydrocarbon radical and each X is chlorine, bromine, iodine or hydrogen atom and R1 is a divalent saturated aliphatic hydrocarbon radical, the X atom being attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the silico atom of the said group, the nitrogen atom being attached to the third to the sixth linear carbon atom away from the central silicon atom. R may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl ethoxy methyl, ethoxy ethyl methoxy phenyl, aminomethyl, aminoethy aminohexyl amino octyl p-chlorophenyl or m-bromophenyl. R1 may be radicals containing 3 to 6 linear methylene groups which may be substituted by methyl or ethyl groups. The silanes are prepared by reacting a di-(halogenoalkyl) dihalogenosilane (XR1)2 Si X2 wherein X is halogen with a primary amine RNH2, R and R1 being as defined above, at normal temperatures and pressures as above. Preferably 7 to 10 mols of primary amine are used per mol of silane. Inert hydrogen halide acceptors, e.g. tributyl amine, pyridine and quinoline may be added. Hydrolysis of the spiranes alone yields siloxanes having the unit general formula (RNHR1)2SiO and copolymeric siloxanes containing the unit (RNHR1)2SiO and <FORM:0971233/C3/2> wherein R111 is a monovalent hydrocarbon radical which may be halogenated and n is 0, 1, 2, or 3, are obtained by condensing with known silanes containing hydrolysable groups. The spiranes ma also be cohydrolysed with the nitrogen containing cyclic silanes of general formula <FORM:0971233/C3/3> wherein R11 is a monovalent hydrocarbon radical which may be halogenated, Z is alkyl or phenyl or an ether link and a=0, 1 or 2 described in Specification 946,306 to give copolymers containing (RNHR1)2SiO and <FORM:0971233/C3/4> units; and such compounds may also be condensed with hydroxy end-blocked nitrogen-containing siloxanes of the present invention, e.g. <FORM:0971233/C3/5> to give siloxanes of general formula <FORM:0971233/C3/6> wherein b is at least 1 and R, R1 and R11 are as defined above. In Example 1, di(3-chloro-2-methylpropyl) dichlorosilane and methylamine are heated at 100 DEG C. for 8 hours to give on distillation a product of formula <FORM:0971233/C3/7> which was subsequently hydrolysed to give a siloxane of unit formula <FORM:0971233/C3/8> Many other compounds are prepared and include <FORM:0971233/C3/9> [C6H5NH(CH2)5]SiO; [CH2=CHCH2NH(CH2)6]2SiO; [CH3OCH2CH2NH(CH2)3]2SiO; Copolymers containing (a) (CF3CH2CH2)(CH3)SiO and [CH3CH2NHCH2CH(CH3)CH2]2Si units, (b) [CH3NHCH2CH(CH3)CH2] (CH3)2SiO0.5 and [CH3NHCH2CH(CH3)CH2]2SiO units, and (c) <FORM:0971233/C3/100> The polymers and copolymers may be used as a basis for rubbers and oils, corrosion inhibitors, and as curing agents in polyurethane resins.