Patent GB-701838-A (GB)
Title: A material suitable for use as a lubricant and/or a hydraulic fluid
Filed: 1951-11-13
Abstract: The invention comprises compounds of formula <FORM:0701838/IV(b)/1> where X is R or OR, at least one R being a branched nonyl radicle and any other R's are hydrocarbon radicles.  The branched nonyl radicle preferably has two or more branches, especially three branches.  Many branched nonyl radicles are specified representative being 2, 3, 4-trimethylhexyl, 2, 3-diethylpentyl, 3-ethyl-5-methylhexyl, 3, 5-dimethylheptyl, 2-propyl-3, 3-dimethylbutyl and 2-butyl-3-methylbutyl, 3, 5, 5-trimethylhexyl being preferred. Preferably the nonyl radicle is derived from alcohols made by the oxo synthesis.  The nonyl alcohol may also be made by reacting di-isobutene and formaldehyde in the presence of zinc chloride and hydrogenating the product.  The products are used in lubricant or hydraulic fluid compositions cf. Groups III and XXIX.  Phosphonates may be made by reacting a branched nonyl alcohol with a hydrocarbon phosphonic dichloride in the presence of a hydrogen chloride acceptor such as trimethylamine, pyridine or dimethylaniline.  The hydrogen chloride may also be removed by a current of hot air.  Alternatively a branched nonyl bromide may be reacted with a sodium dihydrocarbon phosphite, e.g. sodium dibutyl phosphite, or a branched nonyl halide may be reacted with p  a trihydrocarbon phosphite, e.g. tributyl or dibutyl nonyl phosphite.  Typical of many specified phosphonates are di-n-butyl 3, 5, 5-trimethylhexane-, bis (3, 5, 5-trimethylhexyl) 2, 4, 4-trimethylpentane-, bis (2, 4, 4-trimethylhexyl) cyclohexane-, bis (4, 4-dimethylheptyl) n-butane-, (3, 5, 5-trimethylhexyl) (2, 4, 4-trimethylpentenyl) 3, 5, 5-trimethylhexane-, and (2, 4, 4-trimethylhexyl) cresyl 3, 5, 5-trimethylhexene-phosphonate. Preferably two branched nonyl radicles are attached to the phosphorus atom by oxygen linkages and the additional hydrocarbon group has 4-12 C atoms.  It is advantageous to have unsaturated branched chain radicles, e.g. branched octenyl radicles, present. Phosphinates containing at least two branched nonyl radicles are made by reacting a branched nonyl alcohol with a hydrocarbon phosphorus dichloride in the presence of a hydrogen chloride acceptor and the phosphonite thus obtained treated with a branched nonyl halide to yield the phosphinate.  Alternatively a branched nonane-phosphorus dichloride is reacted with butyl alcohol in the presence of pyridine to yield dibutyl branched nonanephosphonite which with a branched nonyl bromide yields a butyl bis (branched nonane) phosphinate.  Preferably the two branched nonyl radicles are directly attached to the phosphorus atom.  Typical of many specified phosphinates are 2, 4, 4-trimethylpentyl bis (3, 5, 5-trimethylhexane)-, isopentyl bis (2-ethyl-4-methylhexane)-, n-heptenyl bis (3-butylpentane)-, and 3, 5, 5-trimethylhexyl di-n-butane-phosphinate.  Phosphine oxides containing at least two branched nonyl radicles may be made by forming a Grignard reagent from a branched nonyl bromide and magnesium and reacting the reagent with phosphorus oxychloride or a hydrocarbon phosphoric dichloride.  Typical of many specified phosphine oxides are tris (3, 5, 5-trimethylhexane)-, bis (2, 4, 5-trimethylhexane) 2, 4, 4-trimethylpentene-, bis (3, 5, 5-trimethylhexane) n-butane-and isononane bis (2-ethylhexane)-phosphine oxide.  In examples, (1) 3, 5, 5-trimethylhexanol is reacted with 2, 4, 4-trimethylpentanephosphoric dichloride in the presence of pyridine and toluene to produce bis (3, 5, 5-trimethylhexyl) 2, 4, 4-trimethylpentanephosphonate, (2) 2-ethyl-4-methylhexanol is reacted with 3, 5, 5-trimethylhexanephosphorus dichloride in the presence of pyridine and the resultant phosphonite with 3, 5, 5-trimethylhexyl bromide to yield 2-ethyl-4-methylhexyl bis (3, 5, 5-trimethylhexane) phosphinate, (3) 2, 4, 4-trimethylhexyl bromide is treated with magnesium turnings in ether and phosphorus oxychloride added to produce tris (2, 4, 4-trimethylhexane) phosphine oxide.ALSO:Lubricating oil compositions contain compounds of formula <FORM:0701838/III/1> where X is R or O R, at least one R being a branched nonyl radicle and any other R's are hydrocarbon radicles. The branched nonyl radicle preferably has two or more branches, especially three branches.  Many branched nonyl radicles are specified representative being 2, 3, 4-trimethylhexyl, 2, 3-diethylpentyl, 3-ethyl-5-methylhexyl, 3, 5-dimethylheptyl, 2-propyl-3, 3-dimethylbutyl and 2-butyl-3-methylbutyl, 3, 5, 5-trimethylhexyl being preferred.  Preferably the nonyl radicle is derived from alcohols made by the Oxo synthesis.  The nonyl alcohol may also be made by reacting diisobutene and formaldehyde in the presence of zinc chloride and hydrogenating the product.  Typical of many specified phosphonates are di-n-butyl 3, 5, 5-trimethylhexane-, bis (3, 5, 5-trimethylhexyl) 2, 4, 4-trimethylpentane-, bis (2, 4, 4-trimethylhexyl) cyclohexane-, bis (4, 4-dimethylheptyl) n-butane-, (3, 5, 5-trimethylhexyl) (2, 4, 4-trimethylpentenyl) 3, 5, 5-trimethylhexane-, and (2, 4, 4-trimethylhexyl) cresyl 3, 5, 5-trimethylhexene-phosphonate.  Preferably two branched nonyl radicles are attached to the phosphorus atom by oxygen linkages and the additional hydrocarbon group has 4-12 C atoms.  It is advantageous to have unsaturated branched chain radicles, e.g. branched octenyl radicles, present.  Typical of many specified phosphinates are 2, 4, 4-trimethylpentyl bis (3, 5, 5-trimethylhexane)-, isopentyl bis (2-ethyl-4-methyl-hexane)-, n-heptenyl bis (3-butylpentane)-, and 3, 5, 5-trimethylhexyl di-n-butane-phosphinate.  Preferably the two branched nonyl radicles are directly attached to the phosphorous atom.  Typical of many specified phosphine oxides are tris (3, 5, 5-trimethylhexane)-, bis (2, 4, 5-trimethylhexane) 2, 4, 4-trimethylpentene-, bis (3, 5, 5-trimethylhexane) n-butane-and isononane bis (2-ethylhexane)-phosphine oxide.  The above phosphorous compounds when used in lubricating compositions may be used in conjunction with thickeners such as polymerised acrylic and methacrylic acid esters of molecular weight 5,000-25,000, preferably 5,000-15,000, derived from aliphatic alcohols of 2-15 C atoms, and the polymers may be obtained from single or mixed esters.  Other constituents of the polymer containing composition may be solvents such as kerosene and anticorrosion agents such as sulphur, diaryl disulphides and glycidyl phenyl ether.  About 0.5 to 5 per cent. by weight of thickener is usually required.  Other lubricating compositions described contain the phosphorous compounds together with substances such as glycols, phosphorous esters, alkylene oxide polymers, esters of dicarboxylic acids or hydrocarbons, representative of compounds of the above types specified being ethylene oxidepropylene oxide copolymers, the monobutyl ether of ethylene glycol, polymerised propylene oxide, tricresyl phosphate, bis (2-ethylhexyl) sebacate and kerosene. These substances may be present to the extent of 5-50 per cent. by weight. Small amounts of anticorrosion and antioxidation agents may also be present in amounts generally of 0.05-5 per cent. by weight those mentioned are epoxide compounds such as glycidyl ethers, many of which are specified, isobutyl oxide, pentadiene monoxide, styrene oxide, 2, 3-epoxypentane and epichlorhydrin and sulphur containing organic compounds such as dibenzyl disulphide, di-wax disulphide, dibutyl disulphide and bis (methylene tolyl sulphide).  Gelling agents such as high molecular weight soaps of fatty or hydroxy fatty acids or in organic colloidal materials, e.g. silica, magnesia and alumina may be present, preferably in amounts of 1-10 per cent. by weight when greases or lubricants having thixotropic properties are required.  Example 3 contains a composition of bis (3, 5, 5-trimethylhexyl) 2, 4, 4-trimethylpentene phosphonate with glycidyl phenyl ether and bis (methylenetolyl sulphide).