Patent GB-1056737-A (GB)
Title: Fire-retardants
IPC: C08K5/02
Filed: 1965-07-15
Abstract: Compounds of formula <FORM:1056737/C2/1> wherein X is C=O or SO2 and at least one R has the formula <FORM:1056737/C2/2> wherein Hal is Br or Cl and the other R's -CH2=CH2, are prepared by reacting at 80 DEG to 250 DEG  C. in an inert solvent, preferably in presence of a polymerization inhibitor, compounds of Formula I wherein all R's are -CH=CH2 with at least one mol of hexahalocyclopentadiene, e.g. hexabromo-, dibromotetrachloro-, and hexachloro-cyclopentadiene, or mixtures thereof.  Increased pressure may be used.  Compounds specified are 1,3,5-s-tris-(1,4,5,6,7,7 - hexachlorobicyclo - [2,2,1] - 5-heptenecarboxo - 2) - hexahydrotriazine and 1,3,5 - s - 1 - acryloyl - 3,5 - bis - (1,4,5,6,7,7-hexachlorobicyclo - [2,2,1] - 5 - heptenecarboxo - 2)-hexahydrotriazine.  1,3,5 - s - tris - acryloyl - hexahydrotriazine is prepared by adding conc. H2SO4 to a stirred mixture of acrylonitrile, acetic anhydride, and paraformaldehyde at 60-70 DEG  C., raising the temperature to 70-80 DEG  C. and maintaining after the addition of anhydrous ZnCl2.  1,3,5 - s - tris - (dibromopropionyl) - hexahydrotriazine is prepared by brominating, with bromine dissolved in chloroform, the trisacryloyl compound in chloroform in presence of anhydrous sodium acetate.ALSO:A heat-curable fire-retardant moulding composition comprises an unsaturated polyester and/or polyether acetal, a vinyl co-monomer, a polymerization catalyst active at elevated temperatures, a filler, and a fire-retardant additive which is (A) at least 2% by weight of perchloropentacyclo - (5,2,1,02,6, 03,9, 05,8)-decane or 1,3,5 - s - tris - (dihalopropionyl)-hexahydrotriazine or a mixture thereof or (B) at least 0.2% by weight of a hexahydrotriazine derivative of formula <FORM:1056737/C3/1> wherein X is C = O or SO2 and at least one R is the group <FORM:1056737/C3/2> wherein Hal is Br or C2 and the other R's -CH = CH2, or (C) a mixture of the additives (A) and (B), the additives being present in not more than 30% by weight based on the combined weight of the polyester, polyether acetal and co-monomer.  The composition may also contain antimony trioxide and other flame retardants such as tris-(b -chloroethyl), tris-(dichloropropyl) and tris-(2,3-dibromopropyl) phosphates, and trichloro-, tetrabromo- and pentabromo-diphenyl, zinc stearate as lubricant, and fillers such as textile or glass fibres and mineral powders. The unsaturated polyester may contain halogen, and the polyether acetal may be obtained by adding an ester containing polymerizable double bonds and alcoholic OH groups to diallylidene pentaerythritol or by transesterification of two mols. of 2 - vinyl - 5 - alkyl - 5 - hydroxymethyl-1,3-dioxolane with a dialkyl ester of a dicarboxylic acid.  The comonomer may be styrene, diallyl phthalate or an acrylic or methacrylic ester. Good electrical surface leakage properties are obtained if the bromination of 1,3,5-s-trisacryloylhexahydrotriazine to obtain the corresponding dibromopropionyl compound is effected in neutral or buffered alkaline medium.  In Example 1, a moulding composition comprises an unsaturated polyester from terephthalic acid, maleic anhydride and 1,2 - propylene glycol, perchloropentacyclo-(5,2,1,02,6, 03,9,05,8)-decane, Sb2O3, diallyl phthalate, zinc stearate, t.-butyl perbenzoate, ground limestone and ground kaolin.  Example 2 is similar using as additional fire-retardant 1,3,5-s-tris - (dibromopropionyl) - hexahydrotriazine and containing as fillers magnesium oxide, ground limestone and cut glass fibres.  Example 3 is similar to Example 2, but uses styrene as comonomer.  Example 4 uses 1,3,5-s-tris-(dibromopropionyl) - hexahydrotriazine as sole fire-retardant.  Example 5 uses 1,3,5-stris-(1,4,5,6,7,7 - hexachlorobicyclo - [2,2,1] - 5-heptenecarboxo - 2) - hexahydrotriazine as fire-retardent and benzoyl peroxide as catalyst. In Example 7, the comonomer is styrene and the polyester is modified with dicyclopentadiene. In Example 8, the fire-retardent is 1,3,5 - s - 1 - acryloyl - 3,5 - bis - (1,4,5,6,7, 7-hexachlorodicyclo - [2,2,1] - 5 - heptenecarboxo-2) - hexahydrotriazine and the catalyst a mixture of t.-butylperbenzoate and benzoylperoxide.