Patent GB-807236-A (GB)
Title: Bromine-containing nitrile methylolphosphorus polymers
IPC: C08G79/02
Filed: 1955-11-02
Abstract: A process for producing a polymeric material comprises reacting a phosphorus-containing compound with a nitrogen-containing compound and a bromine-containing compound and continuing the reaction until substantially all the reactants have combined to form a homogeneous polymer, the phosphorus-containing compound being a THP (i.e. tetrakis(hydroxymethyl)phosphonium) salt, THPO or a polymethylol derivative thereof containing at least two methylol groups directly linked to phosphorus, the nitrogen-containing compound having a molecular weight of not more than 800 and containing at least one trivalent nitrogen atom and a plurality of reactive groups which are hydrogen atoms and/or methylol groups and/or terminally-unsaturated alkenyl radicals, each attached to trivalent nitrogen atoms, the bromine-containing compound being a polyfunctional compound which is capable of condensing with formaldehyde and/or esterifying methanol and contains bromine attached to carbon, and the reactants being selected so that they comprise by weight at least 1 per cent of phosphorus present in a phosphonium radical and for every part of phosphorus 0.5 to 20 parts of nitrilo nitrogen in the nitrogen-containing compound, and 0.3 to 15 parts of bromine attached to carbon, substantially all of the reactants being combined in the homogeneous polymer.  "THPC" is an abbreviation for tetrakis (hydroxymethyl) phosphonium chloride ((HOCH2)4PCl) and "THPO" is an abbreviation for tris(hydroxymethyl)phosphine oxide ((HOCH2)3PO). Compounds capable of condensing with formaldehyde or of esterifying methanol are referred to as "Methylol-reacting compounds."  A given compound may fall into more than one of the categories "Phosphorus Compound," "Nitrogen compound" and "Bromine Compound."  The reactants can be monomers or polymeric adducts.  There may be reacted, for example, (1) THPC, melamine and 2,4-dibromohydroquinone; (2) a further polymerizable THPC-urea polymer and 2,3-dibromosuccinic acid; (3) THPO and a partially-brominated diallyl melamine; (4) a further polymerizable THPO - 2,4 - dibromohydroquinone polymer and a further-polymerizable melamine-THPC - 2,3 - dibromosuccinic acid polymer; (5) a bromo derivative of THPC or THPO and THPC and melamine or methylol melamine.  As Phosphorus Compounds there may be used THPC, THPO and compounds obtained therefrom as described in Specification 761,985.  In place of the tetrakis (hydroxymethyl) phosphonium chloride, there can be used the correponding phosphate, acetate, hydroxide or other salt.  Also suitable are compounds of the formulae <FORM:0807236/IV (a)/1> where R represents CH2OH or CH2X and X represents a bromine or chlorine atom.  Other suitable Phosphorus Compounds can be produced by reaction of THPO, THPC or another salts with a compound containing only one H atom or CH2OH group attached to a trivalent nitrogen atom, such as N,N,N1-trimethylethylene diamine, N-butyl cyclohexylamine, methylaniline, diethanolamine, N-allyl acryl amide, N-methyl glycine and brominated derivatives of such compounds, the reaction product containing at least two methylol groups attached to phosphorus atoms.  Specified polyfunctional Methylol-Reacting compounds capable of condensing with formaldehyde are polyamines such as ethylenediamine and tetramethylenepentamine, alicyclic amines, e.g. cyclohexylamine, cyclopentylamine and methylolated cyclohexylamines, aromatic amines such as aniline and phenylene diamines and ethylene imine and its polymers, melamine, guanidine, urea, acrylamide, cyanamide, glycine lysine, arginine and brominated derivatives of such compounds, phenols, and naphthols (which can be hydrocarbon and/or halo-substituted).  As Methylol-Reacting Compounds which will esterify methyl alcohol there are specified various aliphatic, aromatic and alicyclic acids, anhydrides and halides; these may have been reacted with THPO or THPC to give, if containing two methylol-phosphorus groups, suitable "Phosphorus Compounds." Particularly suitable as Nitrogen Compounds are N-alkenyl melamines, especially those with at least one bromine atom attached to carbon and at least two active hydrogens (as H or CH2OH) attached to trivalent nitrogen atoms.  Such brominated derivatives are obtained by reacting an N-alkenylated melamine with a polyhalohydrocarbon (capable of reacting, by addition, with an olefin) and, if desired, an aldehyde.  Preferred N-alkenyl melamine or acrylamide adducts of polyhalohydrocarbons are those produced from compounds of the formula CX2Y2 in which X represents a bromine or chlorine atom and Y represents a bromine, chlorine or hydrogen atom.  The products of the invention are suitable for the production of buttons, insulators, coatings, adhesives, and especially as flame-proofing agents for textiles.  In the latter application they can be employed as solutions or emulsions and insolubilized by heating or treatment with ammonia, or they can be formed in situ.  In examples: (1) a dispersion of N,N1-diallylmelamine in water containing formaldehyde, polyvinyl alcohol and sodium carbonate is reacted with bromoform in the presence of potassium persulphate.  A sample of twill is treated with an emulsion of the product containing also as resin-forming reactants THPC, urea, a water-soluble methylolmelamine and triethanolamine, then dried at 100 DEG  C. followed by heating at 140 DEG  to cure the resin; (2) a brominated diallylmelamine in neutralized formaldehyde solution is mixed with a solution of the resin-forming reactants specified in Example (1), applied to a cotton twill and cured by heating at 140 DEG ; (3) a similar process to (2) is effected using a bromoform/acrylamide reaction product. Specifications 740,269, 761,195, 764,312, 764,313, 764,314, 775,325 and 790,641 also are referred to.ALSO:As intermediates for synthetic resins there are prepared phosphorus compounds of the formulae <FORM:0807236/IV (b)/1> where R represents CH2OH or a CH2X radical and X represents a bromine or chlorine atom.  Such compounds are obtained by reacting tetrakis (hydroxymethyl) phosphonium chloride (THPC) and tris (hydroxymethyl) phosphine oxide (THPO) with halogenating agents such as hydrobromic acid, phosphorus pentachloride or bromide or phosphorus trichloride or tribromide. Other suitable phosphorus compounds are prepared by reacting THPO, THPC or other salt with a compound which contains only one H atom or CH2OH group attached to a trivalent nitrogen atom, such as open polyamines, e.g. N,N,N1-trimethyl ethylenediamine, alicyclic amines, e.g. N-butyl cyclohexylamine, aromatic amines, e.g. methylaniline, heterocyclic amines, e.g. pyrrole, aliphatic amines, e.g. diethanolamine, amides, e.g. N-allyl acrylamide, amino acids, e.g. N-methyl glycine, and brominated derivatives thereof, the resulting compounds containing at least two CH2OH groups attached to phosphorus.  Suitable brominated alkenyl-melamine intermediates containing at least one bromine atom attached to carbon and at least two members of the group H and CH2OH, e.g. N,N-bis (2,3-dibromopropyl) melamine are prepared by bromination of the appropriate alkenyl melamines.  In an example diallyl melamine in acetic acid is brominated to give a crystalline product. Specifications 740,269, 761,195, 761,985, [all in Group IV (a)], 764,312, [764,313, 764,314, 775,325 and 790,641, [all in Group IV (a)]], are referred to.