Patent GB-877905-A (GB)
Title: Improvements in or relating to phosphoric acid ester derivatives of hydroxyalkyl or hydroxycycloalkyl esters of ª-,ª--ethylenically unsaturated monocarboxylic acids
IPC: D06M15/356
Filed: 1958-03-25
Abstract: The invention comprises polymers containing units of the formula: <FORM:0877905/IV (a)/1> wherein R is hydrogen, chlorine or a methyl group, R1 and R2 each represent a C1-C4 alkyl group or a C1-C4 halogen-substituted alkyl group in which each halogen substituent is chlorine or bromine and is attached to a carbon atom other than one bonded directly to oxygen, and A is a divalent saturated aliphatic or cycloaliphatic hydrocarbon group, said hydrocarbon group containing not more than 6 carbon atoms and providing a chain of at least two carbon atoms between the two adjacent oxygen atoms.  The polymers may be obtained by polymerizing under the influence of a free-radical polymerization initiator such as a peroxide or azo compound, a monomeric compound of the formula:  <FORM:0877905/IV (a)/2> wherein A, R, R1 and R2 are as defined above, (see Group IV(b)) either alone or with one or more other copolymerizable ethylenically unsaturated compounds, particularly those containing a <FORM:0877905/IV (a)/3> group, e.g. esters of acrylic or methacrylic acid or methacrylic acid itself.  Examples are given for the production of (1) a copolymer of dimethylphosphatoethyl methacrylate and methyl methacrylate; (2) a terpolymer of diethylphosphatoethyl methacrylate, methyl methacrylate and methacrylic acid; (3) a terpolymer of diethyl phosphatoethyl methacrylate, methyl methacrylate and bromoethyl methacrylate; (4) a polyester resin compound obtained by heating a mixture of diethylphosphatoethyl methacrylate, bromoethyl methacrylate, styrene, and a solution of a polyester (derived from maleic and phthalic anhydrides and propylene glycol) in methyl methacrylate in the presence of benzoyl peroxide dispersed in tricresyl phosphate; and (5) a terpolymer of diethylphosphatoethyl acrylate, methyl methacrylate and methacrylic acid.  The products have flame-retardant properties and can be used to impart such properties to textile and other fibrous materials, e.g. leather.  Specification 595,881 is referred to.ALSO:The invention comprises compounds of the general formula <FORM:0877905/IV (b)/1> in which R is hydrogen, chlorine or a methyl group, R1 and R2 each represent a C1-C4 alkyl group or a C1-C4 halogen-substituted alkyl group in which each halogen substituent is chlorine or bromine and is attached to a carbon atom other than one bonded directly to oxygen, and A is a divalent saturated aliphatic or cycloaliphatic hydrocarbon group, said hydrocarbon group containing not more than six carbon atoms and providing a chain of at least two carbon atoms between the two adjacent oxygen atoms.  They may be obtained by reacting together a hydroxy compound CH2=C(R)-CO.O.A.OH with a compound of the formula Q.P(O)(OR1)(OR2) wherein Q is a halogen atom other than fluorine or is an OR1 group.  When Q is halogen other than fluorine the reaction is preferably carried out in the presence of a hydrogen halide acceptor and an inert solvent may be present.  In an alternative procedure the hydroxy compound is reacted with a secondary ester of phosphorous acid of the formula HP(O)(OR1)(OR2) in the presence of an aliphatic polyhalide in which the halogen is chlorine, bromine or iodine e.g. carbon tetrachloride or tetrabromide or bromotrichloromethane the reaction being preferably effected in the presence of a hydrogen halide acceptor, e.g. a tertiary amine. Examples are given for the production of diethylphosphatoethyl acrylate and methacrylate, diethyl (and dimethyl) phosphatopropyl methacrylates and dimethyl phosphatoethyl methacrylate.  The products can be polymerized either alone or with one or more copolymerizable compounds to yield products having good flame-retardant properties (see Group IV(a)).  Specification 595,881 is referred to.