Patent GB-474234-A (GB)
Title: Manufacture of valuable oils from vinylacetylene
Filed: 1936-04-24
Abstract: Vinylacetylene is reacted with hydrogen in the presence of a hydrogenation catalyst and in the presence or absence of a solvent, oily constituents of a carbon content higher than C4 being isolated from the solvent or the reaction gases. Suitable catalysts comprise Pa, Ni, Pt, Co, Cu, Ru and Fe. Partially or completely hydrogenated products are obtained depending on reaction conditions.  Crude acetylene polymer mixtures may be utilized, the divinylacetylene and higher polymers present also reacting.  The oil produced is removed continuously or intermittently.  If reaction is effected in the gaseous phase, dilution with, e.g. nitrogen, steam, hydrocarbon vapour, or a fine spray of indifferent liquid may be used to consume reaction heat. Preferably, a liquid is present which may be a non-solvent for the oil, e.g. water or polyhydric alcohols, a solvent therefor, or the oil itself.  With water or aqueous solutions the oil may be removed after separation or extracted with, e.g. ether or benzene. If solvents are used separation by distillation or addition of a third liquid may be used.  Separation from water-soluble lower alcohols, e.g., is effected by adding water or calcium chloride solution.  Strongly unsaturated oils may be further hydrogenated. The unsaturated oils may be separated into fractions of different boiling range or may be further polymerized to oily or resinous products which can also be hydrogenated.  They are used as drying oils, absorbing oxygen to form films of the linoxyn type.  Driers, softening agents, and other known varnish or lacquer materials, e.g. linseed or wood oil, and polymerization products of styrene, vinyl compounds, or acrylic acid esters, may be added.  In examples: (1) a mixture of 3 vols. vinylacetylene to 2 vols. H2 is passed into a column of liquid such as isopropyl alcohol containing palladium on a finely distributed carrier and if desired a substance accelerating the gas distribution, e.g. an oxyalkylamine.  The oily condensation product is removed in the liquid and separated by adding water, salt solution, a polyhydric alcohol or the like; (2) a vinylacetylene, hydrogen mixture is passed through a tower wherein a solvent such as acetone, cooled to 10--15 DEG  C., circulates.  Palladium on pumice stone is a suitable catalyst; (3) aqueous alcohol or pyridine is used in the process of (2), oil separating in a collecting vessel through which the solution passes; (4) water is the circulating liquid, the separating oil being continuously drawn off; (5) oil obtained in the reaction is used in the process of (2); (6) the process of (1) or (2) is carried out at 50--60 DEG  C.; (7) pure or crude vinylacetylene and hydrogen are treated with a suspension of active Pa in alcohol in a "Stöder" washer, e.g. at 25 DEG  C.  The vinylacetylene may alternatively be introduced separately in liquid state or in solution; (8) the reacting gases with 5--10 times their volume of steam are passed over active Ni; (9) an unsaturated oil is hydrogenated until its iodine number is halved; (10) the product of any of examples (1)--(8) is polymerized by heating in N2 at about 220--230 DEG  C.; (11) polymerization is effected in an autoclave at 200--220 or at 250 DEG  C.; (12) the drying period of a strongly unsaturated oil, viz. 12--24 hrs., is reduced to 3 hrs. by addition of 1 per cent of Pb, Mn or Co naphthenate; (13) the viscous product of (10) or (11) is used as a varnish; (14) 1--2 per cent of wool fat is added as softening agent to the varnishes of (12) or (13); (15) a varnish consists of equal quantities of an oil obtained by any of examples 1--11 and linseed oil.ALSO:Condensation products having a carbon content higher than C4 obtained by reaction of vinylacetylene with hydrogen in the presence of a hydrogenation catalyst are used as drying oils. They may be separated into fractions of different boiling range or further polymerized.  Strongly unsaturated products may be further hydrogenated before or after polymerization. Varnishes or lacquers containing the products may include driers, softening agents, linseed or wood oil, or other polymerization products. In an example, 1--2 per cent of wool fat is added as softening agent.  A varnish consists of equal quantities of the condensation product, if desired after further hydrogenation or polymerization, and linseed oil.