Patent GB-413637-A (GB)
Title: A process for improving hydrocarbons, in particular lubricating oils
IPC: C10M145/08
Filed: 1933-01-13
Abstract: Paraffin waxes and hydrocarbon lubricating oils and greases are improved by addition of a small proportion, e.g. 0,5--10,0 per cent of one or more highly polymerized vinyl compounds containing oxygen, i.e. polymers of m.w. about 1,000 but preferably 3,000--10,000.  The waxes become softer, and are less liable to acquire fissures, and are thus suitable for making candles.  The lubricants have their pour points lowered, and their viscosity indices raised.  The polymers may be formed in the wax, oil or grease, or in other oils to be added thereto; other polymerizable substances, e.g. iso-olefines may be present; and the polymers may be hydrogenated or otherwise modified chemically.  There may also be added to the oils or greases substances lowering the setting point, e.g. highly polymerized iso-butylene, voltalized paraffin or other wax, and condensed hydrocarbons obtained as described in Specification 349,071; castor oil miscible with mineral oils; dioleyl-ketone; methyl-oleyl-ketone; glycol ester of ricinoleic acid; oleic acid ester of methyl glycol; hydrocarbons, e.g. naphthalene, oil fraction and residues, paraffin wax.  Vinyl polymers specified are those of:--vinyl esters of oleic, stearic, and palmitic acids; vinyl carboxylic acids or esters, e.g. acrylic acid, acrylic acid octodecyl ester; vinyl ethers of unsaturated alcohols or mixed unsaturated and saturated alcohols, e.g. butyl, octodecyl, oleic, cetyl, and industrial alcohols; and vinyl-ethyl, vinyl-phenyl, and vinyl-cyclohexyl ethers.  In examples: (1) a mixture of 1--3 lb. of vinyl octodecyl ether and 1 lb. of vinyl butyl ether is polymerized by the double compound of boron fluoride and ether dissolved in dibutyl ether; 0,1, 0,5, or 1,0 per cent is added to a lubricating oil.  (2) The vinyl ether of oleic alcohol obtained from sperm oil is polymerized as described in Specification 378,544 by heating to 50 DEG  C. in presence of boron fluoride or a dilute solution in dibutyl ether of the addition compound of boron fluoride and dibutyl ether; 0,1, 0,3, or 1,0 per cent is added to lubricating oil.  The effect is increased by heating the polymer to 300 DEG  C., for 3 min. (3) 150 gm. of the vinyl ether of a cetyl alcohol containing unsaturated alcohols is mixed and warmed gently with 350 gm. of mineral lubricating oil, and polymerized by the addition of boron fluoride-dibutyl ether double compound and stirring in a water-bath at 30--50 DEG  C. to prevent increase of temperature above 70 DEG  C.  When the reaction is complete the mixture is allowed to stand at room temperature, washed with dilute caustic soda and hot water, and dried in vacuo at 100 DEG  C.; 0,3, 0,5, 1,0, or 3,0 per cent. is added to lubricating oil.  (4) Polymerized vinyl phenyl ether is hydrogenated at 180--200 DEG  C. in presence of nickel to form polymerized vinyl cyclohexyl ether.  The Provisional Specifications refer also to Specifications 379,717 and 401,297, [Group IV], and specify the treatment of high molecular hydrocarbons in general, including benzine, illuminating oil, gas oil, and candle waxes.  Specification 402,513 also is referred to.ALSO:Highly polymerized vinyl compounds containing oxygen, i.e polymers of m.w. about 1000 but preferably 3000--10,000 are used to improve hydrocarbon lubricants and paraffin wax.  The polymers may be formed in the wax or lubricant or in oils to be added thereto; other polymerizable substances, e.g. iso-olefines may be present, and the polymers may be hydrogenated or otherwise modified chemically. Polymers specified are those of:--vinyl p  esters of oleic, stearic, and palmitic acids; vinyl carboxylic acids or esters, e.g. acrylic acid, acrylic acid octodecyl ester; vinyl ethers of unsaturated alcohols or mixed unsaturated and saturated alcohols, e.g. butyl, octodecyl, oleic, cetyl, and industrial alcohols; and vinyl-ethyl, vinyl-phenyl, and vinyl-cyclohexyl ethers.  The polymers may be prepared by polymerization of the monomeric compounds or mixtures thereof, e.g. by boron fluoride, boron trichloride, zinc chloride, aluminium chloride, peroxides, e.g. benzoyl peroxide, or the double compounds of boron fluoride with ethers as described in Specification 378,544; or by chemical conversion of other polymerized vinyl compounds, e.g. the reaction of polymerized vinyl alcohol with aldehydes or stearic acid.  For example, the vinyl ether of oleic alcohol obtained from sperm oil is polymerized at 50 DEG  C. in presence of boron fluoride or a dilute solution in dibutyl ether of the addition compound of boron fluoride and dibutyl ether.  The polymer may be further heated to 300 DEG  C. for 3 min.  Or vinyl ether of cetyl alcohol containing unsaturated alcohols is mixed with mineral lubricating-oil, and stirred in a water-bath at 30--50 DEG C. to prevent the temperature rising above 70 DEG  C.; when the reaction is finished the mixture is allowed to stand at room temperature, washed with dilute caustic soda and hot water, and dried in vacuo at 100 DEG  C.  The boron fluoride may be diluted with nitrogen or carbon dioxide or other inert gas, and the polymer may be purified with steam.  The hydrogenation of the polymers may be effected at 180--200 DEG  C. in presence of nickel.  Thus polymerized vinyl phenyl ether is hydrogenated to form polymerized vinyl cyclohexyl ether. Specification 402,513, [Group III], also is referred to.