Patent GB-697684-A (GB)
Title: Improvements in or relating to siloxanes
IPC: C08G77/00
Filed: 1951-04-25
Abstract: The invention comprises polysiloxanes having the unit structure: <FORM:0697684/IV (a)/1> wherein a has a value from 0 to 2, n has a value from 0 to 2, R represents an alkyl or phenyl radical, and R1 represents an p  alkyl, alicyclic or phenyl radical, salts of the above polysiloxanes having the unit structure:  <FORM:0697684/IV (a)/2> wherein a1 has a value from 0 to 3, n has a value from 0 to 2, Y is an inorganic acid anion, Y being chlorine when a1 is 3, and R and R1 have the above significance, and copolysiloxanes in which at least 0.1 mol. per cent of the siloxane units have the unit structure given above, the remaining siloxane units having the unit structure <FORM:0697684/IV (a)/3> , where n1 has a value from 0 to 3, and R11 represents an alkyl, monocyclic aryl hydrocarbon or halogenated monocyclic aryl hydrocarbon radical, there being in the copolysiloxanes an average of from 0.9 to 3 of the above defined organic radicals per silicon atom.  The polysiloxanes may be prepared by any of the following methods: (a) reacting the required polysiloxane containing one halogenomethyl radical per silicon atom with ammonia or an amine under anhydrous conditions, the halogen being preferably bromine or chlorine; the reaction may be carried out at a temperature from 50 DEG  to 150 DEG  C., and in the case of a volatile amine, under an elevated pressure; (b) hydrolysing an amine of the general formula R3SiCH2NR1aH2-a, where at least one R represents an alkoxy radical, the remaining R radicals, R1 and a having the above significance, the said hydrolysis being preferably carried out in a basic medium; (c) treating a trimethylsilylmethylamine with concentrated sulphuric acid at a temperature from 50 DEG  to 115 DEG  C.  The salts are prepared by the reaction of inorganic acids with the polysiloxanes referred to above, and by reacting tertiary amines containing alkyl, alicyclic or phenyl radicals with the required chloromethylpolysiloxanes.  The siloxanes may be polymeric siloxanes in which each silicon atom has only one organic radical attached thereto by a carbon to silicon linkage, said radical being of the formula (R1aH2-aNCH2) referred to above, or may be polymeric siloxanes in which the polymer units are of the general formula (R1aH2-aNCH2)RSiO, where R, R1 and have the significance indicated above.  In the examples: (1) bis-(N-cyclohexylaminomethyl) tetramethyldisiloxane is prepared by treating N-(trimethylsilylmethyl) cyclohexylamine with concentrated sulphuric acid and may be converted to the dihydrochloride salt; (2) bis-(N - isopropylaminomethyl) tetramethyldisiloxane is prepared as in (1) from N-isopropyl (trimethylsilylmethyl) amine and is converted to the dihydrochloride salt; (3) a quaternary salt of the formula Cl(Me3NCH2Me2SiOSiMe2CH2NMe3)C is prepared by treating bis-chloromethyltetramethyldisiloxane with trimethylamine; (4) a polymeric siloxane having the unit formula (NH2CH2)CH3SiO is prepared by hydrolysing diethoxymethylsilylmethylamine with water, and the polymer takes up carbon dioxide from the atmosphere to form a polymer having the unit formula (H2CO3.H2NCH2)CH3SiO; (5) bis - (isopropylaminomethyl) - tetramethyldisiloxane is prepared by heating isopropylamine and bis-chloromethyltetramethyldisiloxane under pressure and is converted into the dihydrochloride salt; (6) a polymeric siloxane having the unit formula H2NCH2SiO3/2 and containing some silicon bonded hydroxyl groups is obtained by adding water to triethoxysilylmethylamine; (7) a copolymer containing the units (NH2CH2)C6H5SiO and (CH3)2SiO is obtained by hydrolysing with water equimolecular proportions of diethoxyphenylsilylmethylamine and dimethyldiethoxysilane.ALSO:The invention comprises organo-silicon compounds having the unit structure <FORM:0697684/IV (b)/1> wherein a has a value from 0 to 2, n has a value from 0 to 2, R represents an alkyl or phenyl radical, and R1 represents an alkyl, alicyclic or phenyl radical, and salts of the above compounds which have the general formula <FORM:0697684/IV (b)/2> wherein a1 has a value from 0 to 3, n has a value from 0 to 2, R and R1 have the above significance and Y is an inorganic acid anion, Y being chlorine when a1 is 3.  The group R may be the methyl, ethyl, isopropyl, octadecyl or tertiarybutyl radical, and the group R1 may be the methyl, propyl, isopropyl, octadecyl, cyclohexyl, cyclopentyl or methylcyclohexyl radical.  The organo-silicon compounds may be prepared by any of the following methods: (a) Reacting the required siloxane containing one halogenomethyl radical per silicon atom with ammonia or an amine under anhydrous conditions, the halogen being preferably bromine or chlorine; the reaction is preferably carried out at 50 DEG  to 150 DEG  C., and in the case of ammonia and volatile amines, under elevated pressures.  (b) Hydrolyzing an amine of the general formula R3SiCH2NR1aH2-a, where at least one R is an alkoxy radical, the remaining R's, R1 and a having the above significance, the said hydrolysis being preferably carried out in a basic medium.  (c) Treating a trimethylsilylmethylamine with concentrated sulphuric acid at a temperature from 50 DEG  to 115 DEG  C.  The salts referred to above are prepared by the reaction of inorganic acids with the above siloxanes to form the acid addition salts, and the quaternary salts are formed by reacting tertiary amines containing alkyl, alicyclic or phenyl radicals with chloromethylsiloxanes.  The siloxanes may be polymeric siloxanes in which each silicon atom has only one organic radical attached thereto by a carbon-to-silicon linkage, said radical being of the formula (R1aH2-aNCH2) referred to above, or may be polymeric siloxanes in which the polymer units are of the general formula (RaH2-aNCH2)RSiO, where R, R1 and a have the significance indicated above, or may be disiloxanes of the general formula <FORM:0697684/IV (b)/3> where R, R1 and a have the significance indicated above. In the examples: (1) bis (N-cyclohexylaminomethyl) tetramethyldisiloxane is prepared by treating N-(trimethylsilylmethyl) cyclohexylamine with concentrated sulphuric acid and may be converted to the dihydrochloride salt; (2) bis-(N-isopropylaminomethyl) tetramethyldisiloxane is prepared as in (1) from N-isopropyl (trimethylsilylmethyl) amine and is converted into the dihydrochloride salt; (3) a quaternary salt of the formula <FORM:0697684/IV (b)/4> is prepared by treating bis-chloromethyltetramethyldisiloxane with trimethylamine; (4) bis-(isopropylaminomethyl) tetramethyldisiloxane is prepared by heating isopropylamine and bis-chloromethyltetramethyldisiloxane under pressure and is converted into the dihydrochloride salt. Specification 686,068 is referred to.