Patent GB-1067751-A (GB)
Title: Organic compounds containing phosphorus-nitrogen linkages
Inventor: HASZELDINE ROBERT NEVILLE
IPC: C08G79/02
Filed: 1962-07-10
Abstract: The invention comprises compounds containing <FORM:1067751/C2/1> repeating units where R represents hydrogen, halogen or an alkyl, aryl, substituted alkyl or substituted aryl radical, and preferably a fluorinated C1-C4 alkyl radical.  They may be prepared by reacting ammonia or a primary amine R1NH2, where R1 is a non-reactive alkyl, aryl, substituted alkyl or substituted aryl radical with a primary a -a -dihalogenoalkyl phosphine having the formula R.CX2.PH2, where X represents halogen, whereby two molecules of hydrogen halide are eliminated for each molecule of primary phosphine consumed.  The reaction may be carried out in the gas or liquid phase or in an inert solvent.  The ratio of the reactants can vary from 1 : 5 to 10 : 1 for the molar ratio of ammonia or primary amine to primary phosphine. The reaction conditions can be controlled so that in the reactions of primary amines with primary halogenated alkyl phosphines cyclic compounds may be isolated of general formula (-NR1-PCH2R-)n, where n is 2, 3 or 4.  When n is greater than 4 linear polymers may be isolated.  The cyclic compounds may have the formulae <FORM:1067751/C2/2> On reaction of ammonia with primary halogenated alkyl phosphines a polymer having an empirical formula (R.CH2P)3N2 is produced, although products having a formula (R.CH2 P-NH)n analogous to those obtained with primary amines may be obtained by suitable control of the reaction conditions.  If the group RCX2 of the primary phosphine RCX2PH2 contains a halogen on the carbon atom of the group R, loss of hydrogen halide from the RCH2 group of the polymers or non-polymeric compounds (RCH2P)3N2, (RCH2P.NR1)n may occur when an excess of ammonia or primary amine is used.  Vinyl compounds of the type (>C = CHP)3N2, (>C = CHPNR1)n are thus produced.  Reactions described include those of ammonia with each of the following: 1,1,2,2-tetrafluoroethyl phosphine, trifluoromethyl phosphine and 2-chloro-1,1,2-trifluoroethyl phosphine; and the reaction of each of methylamine and aniline with 1,1,2,2-tetrafluoroethyl phosphine.ALSO:The invention comprises polymers containing <FORM:1067751/C3/1> repeating units, wherein R is hydrogen, halogen or an alkyl, aryl, substituted alkyl or substituted aryl radical. They may be obtained by reacting ammonia and/or a primary amine R1NH2, where R1 is a non-reactiv alkyl, substituted alkyl, aryl or substituted aryl radical, with a primary a ,a -dihalogenoalkyl phosphine of the formula R.CX2.PH2, where X is halogen, whereby two mols of hydrogen halide are eliminated for each mol of primary phosphine consumed.  When ammonia is used as a reactant the polymeric product may have a cross-linked structural formula, a linear structural formula, or a mixture of structural types.  When ammonia and a primary amine R1NH2 are together used as reactants intermediates of the formula <FORM:1067751/C3/2> may be obtained which homopolymerize in a linear manner.  If the carbon atom of the group R which is attached to the CX2 group of the phosphine bears a halogen atom, loss of hydrogen halide may occur when an excess of ammonia or primary amine R1NH2 is used, resulting in the formation of vinyl compounds of the type (>C=CHPNR1)n, where n is an integer greater than one.  Examples are given for the production of polymeric compounds.