Patent GB-1033252-A (GB)
Title: Halogen-containing organic di-phosphate derivatives and compositions containing them
IPC: C07F9/6574
Filed: 1963-03-06
Abstract: Halogenated diphosphate esters having the general formula <FORM:1033252/C4-C5/1> wherein Z1, Z2, Z3 and Z4 are the same or different and are selected from Cl or Br or from groups of the formula -O-CH(R1)CHXR, wherein each X is Cl or Br, R is H, hydrocarbyl, halohydrocarbyl, hydrocarbyloxyalkyl or hydrocarbyl C(O)O alkyl and R1 is H, C1-C6 alkyl or C1-C6 haloalkyl, R1 being H when R is hydrocarbyloxyalkyl or hydrocarbyl C(O)O alkyl are useful as pre-ignition-inhibiting agents in organo-lead-containing hydrocarbon fuels, e.g. gasolines, and as additives to hydrocarbon-based lubricating oil compositions.  They are also useful for incorporation in natural resins, e.g. shellac, copal, damar, pine balsam or rosin whereby the resins are modified or flame-proofed.ALSO:The invention comprises compounds of the general formula <F\1> wherein each X is Cl or Br and compounds of the general formula <F\2> wherein each X is chlorine or bromine, R is hydrogen, hydrocarbyl, halohydrocarbyl, hydrocarbyloxyalkyl or hydrocarbyl C(O)O Alkyl, and R1 is hydrogen, C1-C6 alkyl or C1-C6 haloalkyl, the symbol R1 being hydrogen when R is hydrocarbyloxyalkyl or hydrocarbyl-C(O)O Alkyl.  The compounds of Formula I may be obtained by reacting pentaerythritol with phosphorus trichloride or tribromide and reacting the product with bromine or chlorine and the compounds of Formula II may be obtained by reacting the compounds of Formula I which may be formed by the defined method and may or may not be isolated with an epoxide compound of the formula:-<F\3> wherein R and R1 are as defined above.  The hydrocarbyl radical in the R groups may be aliphatic, aromatic or alicyclic.  The phosphorus-bonded halogen atoms in the compounds I may be replaced step-wise by first reacting with one epoxide compound, e.g. one of higher molecular weight and then reacting with a different epoxide compound, e.g. one of lower molecular weight.  The oxirane compound may be a simple compound such as ethylene- or propylene-oxide or a mixture thereof, epichlorhydrin, epibromhydrin, epifluorohydrin, phenyl glycidyl ether or butadiene monoxide but several other epoxides which may be used are specified including those in which R1 is hydrogen and R is a hydrocarbyloxy, nonterminal epoxides and epoxy-containing esters of unsaturated carboxylic acids having olefinic or acetylenic bonds and by using the latter compounds polymerizable monomers are obtainable. When such polymerizable monomers are desired the reaction should be carried out in the presence of a polymerization inhibitor such as 1,3,5-trinitrobenzene, hydroquinone, hydroquinone monomethyl ether, tannic acidcuprous chloride, phenol or naphthol.  In preparing the compounds I the phosphorus trihalide and pentaerythritol may be mixed in the presence or absence of a solvent or diluent and the mixture warmed until cessation of hydrogen halide evolution.  The resulting reaction mixture is treated with chlorine or bromine generally at - 25 DEG  to 100 DEG  C., preferably at between 0 DEG  and 50 DEG  C., and if desired in the presence of a solvent or diluent until the halogen ceases to be decolorized.  The product, with or without isolation, is then reacted with the epoxy compound at ordinary, decreased or increased temperature, e.g. 0 DEG  to 150 DEG  C., and preferably in the presence of a catalyst, e.g. titanium-, zirconium- or tin-tetrachloride aluminium chloride, ferric chloride, boron trifluoride, iron filings, ammonium metavanadate, phosphorus trichloride or tribromide, pyridine, tri n-butylamine, quinoline, aniline, N,N-diethylaniline or tetrabutyl titanate and an inert solvent or diluent may be present, e.g. benzene, toluene, hexane, heptane, chloroform, carbon tetrachloride, ethylene dichloride, 1,1,2-trichloroethane or chlorobenzene.  In the first step the phosphorus trichloride may be used in excess of the stoichiometric molar proportion of 2: 1 and in the second step the halogen and the pentaerythritol ester of phosphorochloridous or phosphorobromidous acid are preferably reacted in the stoichiometric molar proportion of 2: 1.  Detailed examples are given for the production of 2,2-bis(chloromethyl)-1,3-propylene bis[bis - 2 - (chloroethyl) phosphate], 2,2 - bis(bromomethyl) - 1,3 - propylene bis(2 - bromoethyl 2-chloroethyl phosphate, 2,2-bis(chloromethyl) - 1,3 - propylene bis[bis(2 - chloro - 1-methylpropyl) phosphate, 2,2 - bis(chloromethyl) - 1,3 - propylene bis[bis - 2,3 - dichloropropyl) phosphate, 2,2-bis(bromomethyl)-1,3 - propylene - bis(2 - bromo - 3 - metharcryl-oxypropyl 2-chloropropyl phosphate and a product obtained by reacting pentaerythritol with phosphorus trichloride and then reacting with bromine and ethylene oxide respectively. The products of Formula I may be reacted with alcohols or mercaptans to form esters or with amines to form phosphoramides and are useful as flame-proofing agents for substances having a plurality of hydroxy groups, e.g. cellulosic materials, polyvinyl alcohol, sugars and starches and the products of Formulae I and II are useful as lubricant or gasoline additives and for modifying or flame-proofing natural or synthetic polymeric material (see Divisions C3, C4, C5 and D1).ALSO:Natural and synthetic polymeric materials are modified and/or flame-proofed by incorporating therein a halogen-containing diphosphate ester having the general formula <FORM:1033252/C3/1> wherein Z1, Z2, Z3 and Z4 are the same or different and are selected from Cl or Br or from groups of the formula -O-CH(R1)CHXR wherein each X is chlorine or bromine, R is hydrogen, hydrocarbyl, halohydrocarbyl, hydrocarbyloxyalkyl or hydrocarbyl C(O)O alkyl and R1 is hydrogen, C1-C6 alkyl or C1-C6 haloalkyl, the symbol R1 being hydrogen when R is hydrocarbyloxyalkyl or hydrocarbyl -C(O)O alkyl (see Division C2).  The natural polymeric material may be a starch, e.g. a starch derived from corn, barley, potato or cassava, a natural gum, e.g. agar, gum arabic, psyllium seed, tragacanth and gum karaya, natural rubber, or a protein, e.g. animal glue, casein, wool or leather.  The compounds in which Z1, Z2, Z3 and Z4 are chlorine and/o bromine may also be used as treating agents for substances having a plurality of hydroxy groups, e.g. polyvinyl alcohol, sugars or starches.  Compounds in which R is an unsatuated -C(O)O alkyl radical, e.g. methacryloxy may be polymerized or copolymerized with an acrylic monomer, e.g, acrylic acid, methyl or ethyl acrylate or acrylonitrile, to form novel polymers, e.g. the homopolymer of 1,3-propylene bis - [2 - bromo - 3 - methacryloxypropyl chloropropyl phosphate].  The synthetic polymers in which the halogen-containing phosphates of the given formula may be incorporated may be linear or cross-linked addition or condensation polymers, e.g. polymerized vinyl and vinylidene compounds including polyolefines, polymerized acrylyl compounds such as those derived from acrylic, chloroacrylic and methacrylic acids, and their anhydrides, esters, nitriles and amides; polymers derived from olefinic aldehydes and their acetals; polyvinyl and polyvinylidene halides, polyvinyl alcohol, vinyl ester and N-vinyl imide polymers, polymers derived from: N-vinyl lactams, vinyl aromatic hydrocarbons, vinyl ethers, vinyl-substituted heterocyclic compounds, vinyl or vinylidene ketones or vinylidene cyanide, and copolymers and terpolymers thereof.  Other specified addition polymers are those of a ,b -olefinic dicarboxylic acids and their anhydrides, esters, amides, nitriles and imides including copolymers of maleic anhydride or of a dialkyl fumarate and vinyl compounds, polymers and copolymers of unsaturated cyclic carbonates, polymers and copolymers of compounds having a plurality of double bonds, e.g. conjugated dienes, and of esters of saturated polyhydroxy compounds with olefinic carboxylic acids or of olefinic alcohols with dicarboxylic acids or with olefinic monocarboxylic acids, also polymers of diallyl carbonate, divinyl ether or divinyl benzene. Other polymers mentioned are polyvinyl acetals, hydrolysed polyacrylonitrile and those containing S, P, B or Si, e.g. sulphides, sulphones, sulphoxides, sulphites, sulphates, sulphonates, phosphines, phosphites, phosphates, phosphonates and silanes.  The halogen-containing diphosphate esters are also suitable for modification of or incorporation into liquid polyester resins, e.g. the linear polyesters obtained by reacting one or more polyhydric alcohols with one or more a ,b -unsaturated polycarboxylic acids alone or in combination with one or more saturated polycarboxylic acids or by reacting a linear polyester with a compound containing a CH2 = C< group, e.g. styrene or a substituted styrene; epoxy resins; polyurethanes which may be derived from a wide variety of active-hydrogen containing compounds including polyesters and polyester amides; phenolic resins, e.g. phenolaldehyde resins; aldehyde resins (aminoplasts), superpolyamides (nylons), polypeptides; polymeric lactames, polymeric aldehydes, polyethers, polyesters obtained by the self-condensation of hydroxy acids, polyamides obtained from aminocarboxylic acids, polyanhydrides obtained by self-condensation of dicarboxylic acids, silicon resins, e.g. cross-linked polymeric divinyltetramethyldisiloxane, and cellulose derivatives, e.g. cellulose esters, e.g. cellulose acetate-butyrate, cellulose ethers, cellulose nitrate, carboxymethyl cellulose, rayon and regenerated rayon.  In Example 14, cellulose acetate is blended on hot roll mills with 10-15% of either 2,2-bis-(bromomethyl)-1,3-propylene bis - (2 - bromoethyl 2 - chloroethyl phosphate, or 2,2 - bis - (bromomethyl) - 1,3-propylene bis - (2 - bromo - 3 - chloropropyl 2,3-dichloropropyl phosphate.ALSO:Natural and synthetic polymeric materials are modified and/or fire-proofed by incorporating therein a halogen-containing diphosphate ester having the general formula <FORM: