Patent GB-766722-A (GB)
Title: Improvements in or relating to dialkenyl beta-(carbalkoxy) alkanephosphonates and polymers and copolymers thereof
IPC: C08F30/02
Filed: 1954-09-13
Abstract: The invention comprises polymers and partial polymers of di-beta, gamma-alkenyl-beta-(carbalkoxy) alkane phosphonates of the formula: (R11O)2.P(O).CH2.CHR1.COOR, wherein R is a methyl or ethyl radical, R1 is a hydrogen atom or a methyl radical, and R11 is an allyl or methallyl radical (see Group IV (b)), and copolymers of the said phosphonates with methyl methacrylate, methyl acrylate, diallyl phthalate, vinyl acetate, and an unsaturated polyester resin.  The monomeric phosphonates may also be copolymerized with diallyl benzene phosphonate or acrylonitrile.  The monomers may be polymerized in the presence of an organic peroxide, e.g. benzoyl peroxide, and the copolymerization may be effected by heating the mixtures in the presence of a polymerization catalyst such as an organic peroxy compound, e.g. benzoyl peroxide, acetyl peroxide and tertiarybutyl perbenzoate and may be carried out with mixtures of the monomers in bulk, in a solvent solution, or in an emulsion system.  The degree of polymerization may be controlled to give hard solid resins having flame-resistant properties or viscous liquid partially polymerized products.  Examples are given for the polymerization of diallyl- (and dimethallyl-) beta-carbomethoxy propane phosphonates, diallyl beta-carbomethoxyethane phosphonate, diallyl beta-carboethoxy ethane phosphonate, and diallyl beta-carboethoxypropane phosphonate. Examples are also given for the copolymerization of (1) diallyl beta-cabomethoxy ethane phosphonate with methyl methacrylate; (2) diallyl beta-carbomethoxy propane phosphonate with various proportions of methyl methacrylate, diallyl phthalate, an unsaturated polyester resin, vinyl acetate, and styrene, respectively; (3) dimethallyl beta - carbomethoxypropane phosphonate with methyl methacrylate, diallyl phthalate, an unsaturated polyester resin, and vinyl acetate respectively.  An example is also given in which diallyl beta-carbomethoxy propane phosphonate is partially polymerized by heating with benzoyl peroxide to form a partial polymer which is then further polymerized to a hard, tough, solid resin.  The partial polymers are fusible and soluble in organic solvents and are suitable for use in coating and impregnating solutions for fabrics, further polymerization forming infusible flame-resistant coatings.ALSO:The invention comprises as new products dibeta, gamma alkenyl beta (carbalkoxy) alkane phosphonates of the formula: (R11O)2P(O).CH2.CHR1.COOR, wherein R is a methyl or ethyl radical, R1 is a hydrogen atom or a methyl radical and R11 is allyl or 2-methallyl.  They may be obtained by reacting the corresponding dialkenyl phosphites with alkyl esters of ethylenically unsaturated carboxylic acids of the formula: CH2 = CR1-COOR wherein R and R1 are as defined above in the presence of a sodium alkenolate.  The products may be polymerized or copolymerized with other polymerizable compounds (see Group IV (a)).  In examples: (1) diallyl betacarbomethoxy propane phosphonate is obtained by reacting diallyl phosphite with methyl methacrylate in the presence of a small amount of hydroquinone and a catalyst solution made by dissolving sodium in allyl alcohol and benzene; (2) as in (1) except that trinitrobenzene is also present as polymerization inhibitor and the catalyst solution comprises sodium allylate in allyl alcohol; (3) diallyl beta-carbomethoxy ethane phosphonate is obtained by a process as in (2) except that methyl acrylate is used instead of methyl methacrylate; (4) diallyl beta-carbomethoxy propane phosphonate is obtained by reacting methyl methacrylate and diallyl phosphite in the presence of a catalyst solution prepared by dissolving sodium in a mixture of allyl alcohol and toluene; (5) diallyl beta-carboethoxy ethane phosphonate is obtained by reacting ethyl acrylate and diallyl phosphite while adding a catalyst solution prepared by dissolving sodium in allyl alcohol and toluene; (6) diallyl beta-carboethoxy propane phosphonate is obtained by reacting ethyl methacrylate with diallyl phosphite in the presence of sodium allylate and a small amount of hydroquinone the reaction being carried out in a manner similar to that followed in (5); (7) dimethallyl beta-carbomethoxy propane phosphonate is obtained by reacting methyl methacrylate and dimethallyl phosphite in the presence of a catalyst solution prepared by dissolving sodium in a mixture of methallyl alcohol and toluene. The ester products are slightly viscous liquids which may be used for coating and flameproofing wood or fabrics.