Patent GB-1082013-A (GB)
Title: Halogen containing phosphate esters and their use in the manufacture of flame resistant polymers
Inventor: MOLE MAURICE FREDERICK
IPC: C08G63/692
Filed: 1964-06-05
Abstract: A polymeric material formed by reacting a compound having at least two alcoholic OH groups with a compound having at least two hydroxyl-reactive groups, is modified by the incorporation therein of a compound of the formula <FORM:1082013/C3/1> where R is a C2- 8 haloalkyl group having at least one halogen attached to each carbon other than the a -carbon, each R1 is hydrogen, methyl, chloromethyl or bromomethyl, y is 1-20 and n is 1, or a mixture of the aforesaid compound and a compound of the above formula wherein n is 2.  The polymeric material may be a polyester formed by reacting a di- or polycarboxylic acid or anhydride (or a mixture thereof) with a compound defined above, or with a mixture of polyhydroxy compounds comprising a compound or mixture as defined above, preferably having 2 hydroxyl groups; and preferably with additional polyol, e.g. ethylene glycol, glycerol, tridiethylol propane, pentaerythritol or a polyethylene glycol.  The preferred proportions are one equivalent of additional polyol plus a total of 2 equivalents of acid or anhydride, preferred dicarboxylic acids being maleic, succinic, tetrachlorophthalic and/or phthalic acids, and the uncured polyesters preferably contain from 0.1 to 10% by wt. of P and from 1 to 20% by wt. of halogen. It is preferred to copolymerize the polyester material when unsaturated with from 70 to 80% by wt. of a vinylic compound, e.g. styrene, vinyl chloride and vinyl acetate, in the presence of a conventional polymerization catalyst, e.g. cobalt naphthenate or benzoyl chloride.  Modified polyurethanes may be prepared by mixing an organic polyisocyanate and a compound as described above having at least 2 hydroxyl groups and a molecular weight of at least 150, or a mixture of dihydroxy compounds comprising a compound as defined above and/or a polyester as described above, together with other polyhydroxy compounds, e.g. polyesters and polyethers having molecular weights of from 300 to 8000.  The polyether is preferably a linear polypropylene ether glycol or a condensation product of propylene oxide with a tri-, tetra- or hexa-functional nucleating compound such as glycerol, trimethylol-propane, hexanetriol, pentaerythritol or a hexitol. Other suitable polyethers include mixed condensation products of propylene and ethylene oxides, either with themselves or with a nucleating compound, and polymers of tetrahydrofuran. The polyesters are normally esters of glycols and/or glycerol, trimethylol-propane or pentaerithritol with dicarboxylic acids such as adipic, phthalic or maleic acids, singly or in admixture. The polyesters have at least 2 free hydroxyl groups and preferably have a hydroxyl functionality of from 2 to 4.  In the preparation of polyurethanes, a foam is preferably produced by forming a gas from a foaming agent simultaneously with the urethane polymer under such conditions that the polymer is expanded by the gas.ALSO:Compounds of the formula (RO)nPO[OC2H3R1)yOH]3- n where R is C2- 8 haloalkyl and has at least one halogen atom attached to each carbon other than the a -carbon, each R1 is hydrogen, methyl, chloromethyl or bromomethyl, y is 1-20, and n is 1, or mixtures comprising a compound of the above type and a compound of the above general formula wherein n is 2, may be obtained by reacting a monohaloalkyl acid phosphate or a mixture of mono- and dihaloalkyl acid phosphates of the formula (RO)nPO(OH)3- n with at least sufficient of an alkylene oxide, which is ethylene or propylene oxide, epichlorhydrin and/or epibromohydrin, or a dihydric alcohol, e.g. ethylene, propylene, polyethylene or polypropylene glycol, to substantially complete the esterification of the phosphoric acid. The reaction is suitably effected at 40-85 DEG  C. and a catalyst, e.g. a base or a Lewis acid, may be present, preferred starting materials being b ,g  - dibromopropyl -, b  - chloro - g  - bromopropyl - and b ,g  - dichloropropyl acid phosphates. The products may be used to modify polymeric materials (see Division C3).  The acid phosphate starting material may be obtained by adding P2O5 to a mixture of haloalkanol and water at temperatures below 50 DEG  C.