Patent GB-961443-A (GB)
Title: Organic esters of phosphorus containing phosphonate or phosphinate groups
IPC: C07F9/40
Filed: 1960-07-21
Abstract: The invention comprises organo-phosphorus compounds of the general formulae: <FORM:0961443/C1/1> and <FORM:0961443/C1/2> wherein R is a haloalkyl, haloalkenyl, alkoxy haloalkyl or aryloxyhaloalkyl group having 1 to 12 carbon atoms, R1 is a group having the formula R2 or -OR3 in which R2 is a hydrocarbon or an aliphatic halohydrocarbon group having 1 to 12 carbon atoms or an aromatic halohydrocarbon group having 6 to 12 carbon atoms, R3 is a hydrocarbon or an aliphatic halohydrocarbon group having 1 to 12 carbon atoms, Z is a hydrogen atom or a hydrocarbon, halogenated hydrocarbon, carbalkoxy-hydrocarbon, alkathiohydrocarbon, alkoxyhydrocarbon or cyanohydrocarbon group having 1 to 17 carbon atoms or a furyl or thienyl group and n is an integer which is at least 1. They may be obtained by heating at a temperature of at least 135 DEG C. a compound having one of the general formulae: <FORM:0961443/C1/3> or <FORM:0961443/C1/4> in which R, R1, Z and n are as defined in Claim 1 for a time sufficient for substantial isomerisation to occur. Preferably the heating is carried out at between 165 and 225 DEG C. and in addition to the isomerisation a small amount of intermolecular condensation may take place between the isomerised and unisomerised product with elimination of an alkylene or substituted alkylene dihalide and concomitant production of a compound containing four pentavalent phosphorus atoms. Suitable starting materials for use in the process are the mono- and poly-hydroxymethyl phosphonates disclosed in Specifications 941,706 and 960,368 respectively. Products of particular interest are those of the first given formula above in which R is a haloalkyl group and R1 is a C1-C12 aliphatic halohydrocarbon group. Several examples are given and the products are useful as gasoline and lubricant additives (see Divisions C4 and C5), as rubber compounding chemicals, as adjuvants for synthetic resins and in the preparation of foamed resins (see Division C3), as flame-proofing agents for cellulosic and carbonaceous combustible materials as functional fluids in electrical and force-transmitting applications, and as lubricants, anti-freeze compositions and hydraulic fluids.ALSO:Organo-phosphorus compounds of the general formulae: <FORM:0961443/C3/1> <FORM:0961443/C3/2> wherein H is a haloalkyl, haloalkenyl, alkoxyhaloalkyl or aryloxyhaloalkyl group having 1 to 12 carbon atoms, R1 is a group having the formula R2 or -OR3 in which R2 is a hydrocarbon or an aliphatic halohydrocarbon group having 1 to 12 carbon atoms, or an aromatic halohydrocarbon group having 6 to 12 carbon atoms, R3 is a hydrocarbon or an aliphatic halohydrocarbon group having 1 to 12 carbon atoms, Z is a hydrogen atom or a hydrocarbon, halogenated hydrocarbon, carbalkoxy-hydrocarbon, alkathiohydrocarbon, alkoxyhydrocarbon or cyanohydrocarbon group having 1 to 17 carbon atoms or a furyl or thienyl group and n is an integer which is at least 1 (see Division C2) are used as adjuvants for synthetic resins, e.g. as flame proofing agents or plasticizers. The compounds may be employed in the preparation of phenolic, polyester, polyamide and cellulose ester resins and polymers such as polyvinyl chloride, the polyvinyl acetals, polystyrene, polyethylene, vinyl chloride-vinyl acetate copolymers, the olefin-maleic anhydride copolymers, polybutadiene and the co-polymer elastomers such as butadiene-styrene and butadieneacrylonitrile. They may also be used in the preparation of foamed resins, e.g. polystyrene foam, polyester foams such as polyethylene terephthalate, and the polyurethanes. Specifications 941,706 and 960,368 are referred to.ALSO:A hydrocarbon fuel comprises gasoline, an organo-lead anti-knock compound and a gasoline-soluble organo-phosphorus compound of the general formula <FORM:0961443/C4-C5/1> or <FORM:0961443/C4-C5/2> wherein R is a haloalkyl, haloalkenyl, alkoxyhaloalkyl or aryloxyhaloalkyl group having 1 to 12 carbon atoms, R1 is a group having the formula R2 or -OR3 in which R2 is a hydrocarbo or an aliphatic halohydrocarbon group having 1 to 12 carbon atoms, or an aromatic halohydrocarbon group having 6 to 12 carbon atoms, R3 is a hydrocarbon or an aliphatic halohydrocarbon group having 1 to 12 carbon atoms, Z is a hydrogen atom or a hydrocarbon, halogenated hydrocarbon, carbalkoxy-hydrocarbon, alkathiohydrocarbon, alkoxyhydrocarbon or cyanohydrocarbon group having 1 to 17 carbon atoms or a furyl or thienyl group and n is an integer which is at least 1 (see Division C2).  The gasoline composition may also contain a hydrocarbon halide scavenger, e.g. ethylene dibromide or dichloride, acetylene tetrabromide, a mono- or polyhalopropane, -butane, or -pentane, or a polyhaloalkylbenzene. The organo-phosphorus compounds are also useful as additives for hydrocarbon oil lubricants; also antifreeze compositions or hydraulic fluid or lubricating compositions may be obtained by mixing the organo-phosphorus compounds with partially chlorinated diphenyls, alkylated polystyrenes or polyacrylates. Specifications 941,706 and 960,368 are referred to.