Patent GB-773326-A (GB)
Title: Perfluoro quaternary nitrogen compounds
IPC: D06M13/46
Filed: 1955-04-05
Abstract: The invention comprises perfluoroalkyl carboxylic acid quaternary ammonium alkyl amides of the formula <FORM:0773326/IV(b)/1> where n is 3 to 11, m is 2 to 6, A is an anion and NQ is an oleophilic organic cationogenic group containing a quaternary nitrogen atom, the remaining co-valencies of which are satisfied by means of carbon-nitrogen bonds.  Preferred products are compounds in which -NQ has the structure -N(R)(R1)R11, wherein R1 and R11\h are alkyl groups of 1 to 6 carbon atoms and R is an alkyl, cycloalkyl, alkaryl, aryl or aralkyl group of 1 to 17 carbon atoms, e.g. benzyl, a group (CH2)pCOOH, where p has a value of 1 to 4, or its esters and salts, or a group derived from a dicarboxylic acid such as -CH(COOH).CH2.-COOH or its esters and salts, and compounds wherein NQ is a pyridinium group or wherein the nitrogen atom forms part of a saturated heterocyclic ring such as a piperidine or morpholine ring. The compounds may be made by quaternizing the corresponding tertiary amines, for example by reaction with a halide or sulphate of the formula RA. Compounds wherein -NQ is a pyridinium group are made by reacting pyridine with a perfluoroalkyl-amido-polymethylene halide. The anion A is suitably a halide or sulphate.  The corresponding hydroxides may be made by treating the halide salts with an aqueous suspension of silver oxide.  The compounds are used as surface-active agents.  In examples: (1) N:N-dimethyl-N1-perfluoroctanamidopropylamine is reacted with methyl iodide to give trimethyl gamma-(perfluoroctanamido)-propyl ammonium iodide; (2) beta-perfluoroctanamidoethyl chloride is reacted with pyridine to give beta-perfluoroctanamidoethyl pyridinium chloride; (3) N:N-diethyl-N1-perfluoroctanamidoethylamine is reacted with dimethyl sulphate to make methyldiethyl-gamma - (perfluoroctanamido) ethylammonium methyl sulphate and (4) N:N-diethyl-N1-perfluoroctanamidoethyl amine is quaternated with chloroacetic acid.  Other specified products according to the invention include the perfluoro-hexanoyl derivative of 3-aminopropyldiethyl methyl ammonium iodide, the perfluorooctanoyl derivatives of 3-aminopropyl diethylmethylammonium iodide, 3-aminopropyl dimethyl decylammonium bromide, 3-aminopropyl dimethyl benzylammonium chloride and 2-aminoethyl diethyl methylammonium chloride and the perfluoro-decanoyl and dodecanoyl derivatives of 3-aminopropyl trimethylammonium iodide.  Specification 773,327 is referred to.ALSO:Surface active agents useful as additives for oils and waxes comprise perfluoroalkyl compounds of the formula [CnF2n+1-CONH-(CH2)m-NQ]+A- wherein n has a value of 3 to 11, m has a value of 2 to 6, A is an anion and NQ is an oleophilic organic cationogenic group containing a quaternary nitrogen atom linked to the amide nitrogen atom through a polymethylene chain, the remaining covalencies of the group NQ being satisfied by carbon-nitrogen bonds. Concentrations of 0.1 per cent of the active compound are effective in reducing the surface tension of animal, vegetable and mineral oils and waxes such as petroleum solvents, petrol, paraffin, fuel oils, lubricating oils and paraffin waxes.  The surface tensions of compositions of the active compounds with (a) linseed oil, (b) mineral oil and (c) paraffin wax are listed, the active compounds being perfluorohexanoylaminopropyl N : N - dimethyl - N - ethyl ammonium iodide (n=5, m=3, NQ= N(CH3)2C2H5); perfluorodecanoylaminopropyl trimethylammonium iodide (n=9, m=3, NQ=N(CH3)3); perfluorododecanoylaminopropyl trimethylammonium iodide (n=11, m=3, NQ=N(CH3)3) and corresponding perfluoro-octanoyl quaternary chlorides; bromides; idodides or methylsulphates in which m and NQ have the respective values; 2. N(C2H5)2CH3; 3, N(CH3)3; 3. N(C2H5)2CH3; 3N(CH3)2 C10H21; 3, N(CH3)2CH2C6H5; 2, NC5H4Cl (4-chloropyridinium and 2, N(C2H5)2CH2 COOH.