Patent GB-750505-A (GB)
Title: Oxo-alcohol carbonates and their use as synthetic lubricants and plasticizers
IPC: C07C69/96
Filed: 1953-05-04
Abstract: Mixtures of carbonates of the formula RO-CO-OR1, where R and R1 are residues of oxo alcohols, each having not less than 8, preferably 10-20, carbon atoms per molecule, are used as plasticizers for resins, rubbers and ethyl cellulose.  Specified alcohols are 6-methyl - 1 - heptanol, 2 - n - propyl - 1 - pentanol, 3 - n - propyl - 1 - hexanol, 2,2 - dimethyl-1-octanol, 10,10-dimethyl-1-undecanol, 3-isopropyl-1-heptanol and alcohols obtained in the oxo synthesis from polymers and copolymers of C3 and C4 mono-olefines.  Mention is made also of C8, C11, C13 and C14 alcohols obtained by oxo synthesis. A mixture of carbonates obtained from C13 alcohols may be used to plasticize isobutylene-isoprene copolymers and styrene-butadiene copolymers, the preferred amounts being 15-30 per cent of plasticizer, and to plasticize ethyl cellulose, suitably in a concentration of 10 per cent.ALSO:The invention comprises a mixture of carbonates of formula RO-CO-OR1, where R and R1 are residues of oxo alcohols each having not less than 8 and preferably 10-20 carbon atoms per molecule which may be made by treating the oxo alcohols with phosgene at 260-350 DEG  F., optionally in the presence of solvents such as toluene and preferably in the presence of a base, e.g. tertiary amines and alkali metal hydroxides and carbonates. The reaction may be effected in stages via the chloroformic ester. Specified alcohols are 6-methyl-1-heptanol, 2-n-propyl-1-pentanol, 3 - n - propyl - 1 - hexanol, 2,2 - dimethyl - 1 - octanol, 10,10 - dimethyl - 1 - undecanol, 3 - isopropyl - 1 - heptanol and alcohols obtained in the oxo synthesis from polymers and copolymers of C3 and C4 monoolefines.  C8, C10, C11, C13 and C16 alcohols obtained by oxo synthesis are also mentioned and carbonates from C10, C13 and C16 alcohols described.  In Example (1) a mixture of C13 oxo-alcohols is treated with phosgene to yield the corresponding carbonate mixture. The products are rubber and ethyl cellulose plasticisers and synthetic lubricating oil compositions.ALSO:Synthetic lubricating oils and greases contain a mixture of carbonates of formula RO-CO-OR1, where R and R1 are residues of oxo alcohols, each carbonate having not less than 8 and preferably 10-20, carbon atoms per molecule.  Specified alcohols are 6-methyl-1-heptanol, 2-n-propyl-1-pentanol, 3-n-propyl-1-hexanol, 2, 2-di-methyl-1-octanol, 10, 10-dimethyl-1-undecanol, 3-isopropyl-1-heptanol and alcohols obtained in the oxo synthesis from polymers and copolymers of C3 and C4 monoolefins.  C8, C10, C11, C13 and C16 alcohols obtained by oxo-synthesis are also mentioned. Carbonates with pour points below -20 DEG F. and flash points above 300 DEG F. are preferred.  Pour, flash and viscosity characteristics of carbonate mixtures from C10, C13 and C16 alcohols are described and viscosities of C13 oxo-carbonates containing small amounts of polyacrylate ester or polybutene are tabulated.  Extreme pressure lubricants may be made by adding to the carbonate mixtures, especially those from C10 to C16 alcohols, small amounts, e.g. 2-30 per cent, of an extreme pressure agent containing sulphur, phosphorus and/or halogen such as tricresyl phosphate.  Greases are made by the addition to the carbonate mixture of, e.g. 5-40 per cent of a metal soap, preferably an alkali or alkaline earth metal soap of a fatty acid with 10-30 carbon atoms per molecule or a soap-salt complex consisting of soaps of higher molecular weight fatty acids and salts of fatty acids containing less than 10 carbon atoms per molecule, e.g. acetic, furoic or acrylic acids.  The dry soap or complex may be added to the carbonate mixture which is then heated at 300-500 DEG F. to yield a grease on cooling or the thickening soap or complex may be formed in situ in the mixture by the addition of appropriate fatty acids with heating at 100-200 DEG F. followed by neutralization with a metal hydroxide, preferably caustic alkali, dehydration at 300-400 DEG F. and cooling.  For low temperature grease production the use of lithium soaps or complexes is preferred.  The greases may be modified by the addition of other lubricating oils, particularly synthetic oils, e.g. esters of dibasic acids and complex esters, and other conventional modifying agents such as N-stearyl-p - amino - phenol, phenyl-alpha-naphthylamine, phenothiazine, zinc naphthenate or sulphonate soaps, polybutenes, polyacrylate and polymethacrylate esters, sulphochlorinated hydrocarbons and lead oleate and naphthenate.  Preferred thickeners are lithium soaps or complexes derived from hydrogenated fish oil acids Stabilizers such as the oxides, carbonates or soaps of metals forming amphoteric acids, e.g. zinc, tin and aluminium soaps may also be present.  The preparation of the carbonates is described in Group IV(b).  In examples, (1) a mixture of C13 oxo-carbonates is prepared and a grease obtained therefrom after the addition of a lithium complex of a mixture of acetic and hydrogenated fish oil acids and phenyl-alphanaphthylamine and (2) a grease is made from the mixed carbonates of (1) a lithium soap of a hydrogenated fish oil being formed in situ and di-2-ethyl hexyl sebacate and phenyl-alpha-naphthylamine are also present.ALSO:Rubber is platicized by a mixture of carbonates of formula RO - CO - OR1 where R and R1 are residues of oxo alcohols each having not less than 8, preferably 10-20 carbon atoms per molecule.  Specified alcohols are 6 - methyl - 1 - heptanol, 2 - n - propyl - 1 - pentanol, 3 - n - propyl - 1 - hexanol, 2, 2 - dimethyl - 1 - octanol, 10, 10 - dimethyl - 1 - undecanol, 3 - isopropyl - 1 - heptanol and alcohols obtained in the oxo synthesis from polymers and copolymers of C3 and C4 mono - olefines.  C8, C10, C11, C13 and C16 alcohols obtained by oxo synthesis are also mentioned.  Preferably the plasticizer is present in amounts of 15-30 per cent.