Patent GB-1049023-A (GB)
Title: Improvements in or relating to allyl dihaloalkyl esters of oxyacids of antimony, boron, silicon and titanium and their use as fire-retardant additives for synthetic polyester resins and curable resin compositions
IPC: C07F7/04
Filed: 1964-04-13
Abstract: Complexes of ammonia with SbCl3, SbCl5 and TiCl4 are described in Examples 1, 4 and 7, respectively.ALSO:The invention comprises compounds of the general formula (R1O)aM(OR2)b wherein M is Sb, Ti or B of normal valency, R1 is an allyl radical, R2 is a radical formed from R1 by addition of bromine or chlorine across the olefinic bond, a and b are integers of from 1 to 4 and a + b is an integer of from 3 to 5.  The compounds are prepared by reacting b molar parts of bromine or chlorine with one molar part of a compound of the formula (R1O)a+bM at a temperature of from -30 DEG  to + 25 DEG  C.  The following starting materials are prepared in Examples:  (1) triallyl antimonite, (4) pentaallyl antimonate, and (7) tetraallyl titanate by reaction of allyl alcohol in the presence of ammonia with SbCl3, SbCl5 or TiCl4 respectively (9) triallyl borate by reaction of allyl alcohol with boric acid.  Tetraallyl titanate forms a yellow complex with hydroquinone.ALSO:Fire-resistant, curable polyester compositions comprise (A) 30-83% by weight of the reaction product of (1) 2.0-2.5 molar parts of at least one aliphatic polyhydroxy compound, (2) 0.4-2.0 molar parts of a dibasic carboxylic acid or anhydride containing a polymerizable double bond, and (3) 0-1.6 molar parts of a non-polymerizable dibasic carboxylic acid or anhydride, (B) 15-68% by weight of a monovinyl aromatic solvent for the reaction product (A), and (C) 2-30% by weight of a reactive fire-retardant additive comprising a compound of the general formula (R1O)aM(OR2)b wherein M is Sb, Ti, B or Si of normal valency, R1 is an allyl radical, R2 is a radical formed from R1 by addition of bromine or chlorine across the olefinic bond, a and b are integers of from 1 to 4 and a + b is an integer of from 3 to 5.  The compositions may be cured by adding thereto a free-radical polymerization catalyst and heating until cross-linking takes place.  In a modification, the polyester component (A) may additionally comprise a compound of the formula specified under (C), the allyl groups of which undergo an exchange with the terminal hydroxy groups of the polyester during its formation, and the component (C) may then be present or absent. Specified polyhydroxy compounds are ethylene and propylene glycols and glycerol.  Specified polymerizable acids are maleic, fumaric, itaconic and citraconic acids.  Specified non-polymerizable acids and anhydrides are phthalic, isophthalic, terephthalic, succinic and adipic acids, halogenated derivatives thereof, and phthalic anhydride. Specified monovinyl aromatic compounds are styrene, methyl-styrene and vinyl-pyridine.  The invention also comprises compounds of the general formula (R1O)aSi(OR2)b wherein R1 is an allyl radical, R2 is a radical formed from R1 by addition of chlorine or bromine across the olefinic bond, a and b are integers of from 1 to 3 and a+b is 4.  The compounds are prepared by reacting b molar parts of chlorine or bromine with one molar part of (R1)4Si, which compound may be prepared by reacting SiCl4 with a solution of allyl alcohol and pyridine in carbon tetrachloride.ALSO:In examples, a fibreglass mat is impregnated with a resin solution and then cured in an oven, the resin solution comprising an unsaturated polyester, styrene, a polymerisation initiator and a fireproofing additive of the formula (R1O)aM(OR2)b wherein M is Sb, Ti, B or Si of normal valency, R1 is an allyl radical, R2 is a radical formed from R1 by addition of bromine or chlorine across the olefinic bond, a and b are integers of from 1 to 4 and a + b is an integer of from 3 to 5.  The unsaturated polyesters are those prepared from (a) propylene glycol, fumaric acid and phthalic anhydride, or (b) propylene glycol, trimethylolethane, dibromopropanol, fumaric acid and tetrachlorophthalic anhydride. The polymerization initiators employed are cumene hydroperoxide and benzoyl peroxide.ALSO:In examples, a fibreglass mat is impregnated with a resin solution and then cured in an oven, the resin solution comprising an unsaturated polyester, styrene, a polymerization initiator and a fireproofing additive of the formula (R1O)a M(OR2)b wherein M is Sb, Ti, B or Si of normal valency, R1 is an allyl radical, R2 is a radical formed from R1 by addition of bromine or chlorine across the olefinic bond, a and b are integers of from 1 to 4 and a + b is an integer of from 3 to 5.  The unsaturated polyesters are those prepared from (a) propylene glycol, fumaric acid and phthalic anhydride, or (b) propylene glycol, trimethylolethane, dibromopropanol, fumaric acid and tetrachlorophthalic anhydride. The polymerization initiators employed are cumene hydroperoxide and benzoyl peroxide.