Patent GB-816069-A (GB)
Title: Epoxy-methylol phosphorus derivatives
IPC: C08G59/40
Filed: 1956-06-15
Abstract: In an example (Example 17) a strip of wood is fireproofed by coating with an aqueous solution of a phosphorus-containing polyether prepared by reacting an epoxy resin (EPON 562) with tetrakis(hydroxymethyl) phosphonium chloride, and a small amount of ethylene diamine, and curing at room temperature. Specifications 740,269, 761,985, [both in Group IV (a)], 764,312, [764,313, 764,314, 775,325 and 807,236, [all in Group IV (a)]], are referred to.ALSO:Phosphorus-containing polymers containing 2-hydroxyalkyl ether groups, including modified epoxy resins, are prepared by reacting an epoxy compound with a compound of the formula (RCH2)2P(O)CH2OH or [(RCH2)3PCH2OH]+A-where R is OH or a radical produced by reacting a PCH2OH group with a compound capable of reacting therewith, and A is an anion.  Suitable phosphorus compounds are tris(hydroxymethyl) phosphine oxide (THPO), tetrakis(hydroxymethyl) phosphonium salts, e.g. the chloride (THPC), acetate or dihydrogen phosphate, and their reaction products with methylol reacting compounds, the products containing at least one PCH2OH group.  These products may be monomeric, e.g. formed by reacting THPO or THP salt with a secondary amine, an N-substituted amide, an acid or acid-reacting compound; or they may be polymeric, as formed by reacting with polyfunctional compounds and terminating the reaction before all the PCH2OH groups have reacted, e.g. the further polymerisable nitrilo methylol phosphorus polymers described in Specifications 740,269, 761,985, 764,312, 764,313 and 807,236, the methylol phosphorus alkyds described in Specification 775,325, and the phenolic methylol phosphorus polymers described in Specification 764,314. Instead of using the preformed products, the THP compounds, the methylol reacting compounds and the epoxy compound may all be reacted together.  The epoxy compound may be monomeric or polymeric. Examples are epihalohydrins, ethylene oxide, polyethylene oxides, homologues and analogues of ethylene oxide in which the epoxy group is attached to a hydrocarbon radical (e.g. styrene oxide), and epoxy resins.  The modified epoxy resins, which have enhanced resistance to burning, and, in some case, enhanced fluidity and solubility, may be hardened by the usual acid or amine agents; if free PCH2OH groups are left, they are cross-linked in the same way as terminal epoxy groups. The reaction between the epoxy and phosphorus compounds may be catalysed by acidic or basic catalysts, and may be effected with or without a solvent, e.g. water.  The ethers may be used to stabilize aqueous textile-treating compositions comprising reactants which form nitrilo-methylol-phosphorus polymers.  The examples describe the preparation of ethers from (4) THPC, trimethylolmelamine, urea and epichlorhydrin; (8) THPO and a glycidyl polyether; (9), (10) and (12) to (14) THPC and a glycidyl polyether, using in some cases triethanolamine and butyl carbitol; and in (11) the product of (9) is heated in water with trimethylol-melamine to form an insoluble polymer; in (16) the product of (14) is mixed with ethanol, m-phenylenediamine and asbestos fibre filler and cured at 100 DEG C.; in (17) the product of (14) is mixed with water and ethylenediamine, coated on a wood strip and cured at room temperature.ALSO:The invention comprises phosphorus-containing ethers of the formula (RCH2)2P(O)CH2OCH2CH(OH)R1 or [(RCH2)3PCH2OCH2CH(OH)R1]+A-where A is an anion, R is OH or a radical produced by the reaction of a PCH2OH group with a compound capable of reacting therewith, and R1 is H or an organic radical.  They are prepared by reacting epoxy compounds with compounds of the formula (RCH2)P(O)CH2OH or [(RCH2)3PCH2OH]+A-.  Examples of epoxy compounds are epihalohydrins, ethylene oxide, polyethylene oxides and homologues and analogues of ethylene oxide in which the epoxy group is attached to a hydrocarbon radical (e.g. styrene oxide). Suitable phosphorus compounds are tris (hydroxymethyl) phosphine oxide (THPO), tetrakis (hydroxymethyl) phosphonium salts, e.g. the chloride (THPC), acetate or dihydrogen phosphate; and their reaction products with methylol reacting compounds, e.g. secondary amines, N-subst.-amides, acids or acid reacting compounds.  The reaction may be effected in the presence of basic or acidic catalysts, with or without a solvent. The examples describe the preparation of viscous liquids or solids from (1), (2) and (3) THPC and epichlorhydrin; (6) and (7) THPC and epibromohydrin; (15) THPC and styrene oxide.  Specifications 740,269, 761,985, [both in Group IV (a)], 764,312, [764,313, 764,314, 775,325, [all in Group IV (a)]], and 807,236 are referred to.ALSO:A textile-treating composition, an example of which renders cotton fabric resistant to shrinking and wrinkling, comprises an aqueous mixture of (a) a water-soluble tetrakis (hydroxymethyl) phosphonium salt, tris(hydroxymethyl)-phosphine oxide or a derivative of either of these compounds which contains at least two hydroxymethyl groups attached to each phosphorus atom; (b) a monomeric nitrogencontaining compound which contains at least two members of the group of H and CH2OH attached to trivalent nitrogen, and (c) at least 3 per cent by weight of (a) + (b) of a phosphorus-containing ether compound which is prepared by reacting an epoxy compound with a compound of the formula (RCH2)2P(O)CH2OH or [(RCH2)3PCH2OH] + A -, where R is OH or a radical produced by reacting a PCH2OH or a with a reactive compound, and A is an anion (see Group IV (a)).  The treatment is completed by curing at about 130-170 DEG  C.  The compound (c), which may be monomeric or polymeric, including modified epoxy resins, acts as a stabilizer towards polymerization at ordinary temperatures.  In an example, the composition consists of an aqueous mixture of tetrakis(hydroxymethyl)phosphonium chloride, a water-soluble methylolmelamine, urea, and an epichlorhydrin ether of tetrakis(hydroxymethyl)phosphonium chloride.