Patent GB-950150-A (GB)
Title: New halogen-containing phosphonic acid esters, their preparation and their use
IPC: C08G59/40
Filed: 1962-05-10
Abstract: The invention comprises halogenated phosphonic esters of formula: <FORM:0950150/C2/1> where Hal is halogen, particularly Cl or Br, Y1 to Y4 are each, hydrogen, halogen, particularly Cl or Br, or C1-4 alkyl, and R1 and R2 are each C1-4 alkyl, alkenyl or haloalkyl. They are prepared by reacting a glycidyl ether of formula: <FORM:0950150/C2/2> at elevated temperature with a phosphorous diester or alkali metal salt thereof of formula: <FORM:0950150/C2/3> where M is hydrogen or alkali metal. They are used to impart flame-proofing properties to polyester and epoxy resins (see Division C3).ALSO:Epoxy resins are prepared from epoxy compounds having an epoxy equivalence greater than one and organophosphorus compounds of formula I: <FORM:0950150/C3/1> where Hal is halogen, especially chlorine or bromine, each of Y1 to Y4 is hydrogen, halogen, especially chlorine or bromine, or C1- 4 alkyl, and each of R1 and R2 is C1- 4 alkyl, C1- 4 alkenyl or C1- 4 haloalkyl.  (For preparation see Division C2). Suitable epoxy compounds, of which many are specified, include epoxides derived from cycloaliphatic hydrocarbons and esters, epoxidised polybutadienes and copolymers of butadiene with ethylenic compounds, polyglycidyl esters, e.g. of dicarboxylic acids, epoxides derivable by reacting an amine with epichlorhydrin and alkali, polyglycidyl ethers of polyhydric alcohols and phenols including bis phenols and phenol-formaldehyde condensates. Many specified curing agents include amines, Mannich bases, heterocyclic bases, guanidines, dicyandiamide, urea-, melamine- and aniline-formaldehyde resins, aminostyrene polymers, polyamides, polymeric polysulphides, isocyanates, isothiocyanates, phosphoric acid, polybasic carboxylic acids and anhydrides, polyphenols, phenol-aldehyde resins, reaction products of aluminium alcoholates or phenolates with tautomeric compounds such as acetoacetic ester, Friedel-Crafts catalysts and their complexes, and boroxines. Accelerators may be added, e.g. tertiary amines, quaternary ammonium compounds, metal chelates, alkali metal alcoholates or polyhydroxy compounds.  Plasticizers, inert diluents or active diluents (e.g. mono-epoxides) may also be present. Conventional additives may be included.  Unsaturated phosphorus-containing polyesters are obtained by condensing with heating in any desired order (1) unsaturated di- or polycarboxylic acids or functional derivatives thereof, or mixtures thereof with saturated di- or polycarboxylic acids, (2) diols or polyols and (3) an organophosphorus compound of formula I above. An esterification catalyst and azeotroping agent may be used. Various unsaturated aliphatic and cycloaliphatic acids, acid halides, esters and anhydrides are specified.  Suitable hydroxy compounds include glycols, polyglycols, hydroxyethyl ethers of bisphenols, glycerol, diglycerol and other polyols.  Addition polymers are prepared by polymerizing with a polymerizable monomer either: (1) an unsaturated polyester resin, together with an organophosphorus compound of formula I above; or (2) an unsaturated phosphorus-containing polyester as described in the preceding paragraph.  Suitable polymerizable monomers include styrene, vinyl esters, acrylic esters, acrylonitrile and diallylphthalate.  Organic peroxides are specified polymerization catalysts. A metal drier may be present.  Solvents, plasticizers and other additives may be present.