Patent GB-385963-A (GB)
Title: Improvement in the polymerization of vinylacetylene
Filed: 1931-06-26
Abstract: Oily, gelatinous or resinous products are obtained by polymerizing monovinylacetylene in the absence of other polymerizable substances. Polymerization may be effected by the action of heat in the presence or absence of air; polymerization catalysts and solvents may be present.  Examples 1-11 describe processes in which monovinylacetylene is heated to 80-150 DEG  C. under various conditions to produce non-volatile liquid polymerization products; generally, a partial polymerization is effected, and the unchanged material and volatile products are distilled off at about 100 DEG C.; in examples 5, 8 and 11 benzoyl peroxide is added as a catalyst; in examples 8 and 11 the process is effected continuously in a heated coil through which the vinylacetylene flows; in examples 6, 7 and 11 toluene is present as a solvent; in examples 9 and 10 manganese dioxide and sodium perborate respectively are added as catalysts; the liquid products are unsaturated and are useful as drying oils for paints or varnishes; they form acetylides with cuprous and silver salts.  In examples of the production of gelatinous and solid products, (12) vinylacetylene is heated in a sealed tube to 110 DEG C. with a little benzoyl peroxide, giving a gelatinous product; (13) the process of example 12 is continued for a longer time, giving an insoluble resinous product.  Other catalysts which may be employed are alkali metals, such as lithium, sodium or potassium; alkaline earth metals such as calcium or barium; alloys of the said metals, such as the eutectic of sodium and potassium; halides such as aluminium, zinc or cuprous chloride, stannous or stannic chloride, antimony or arsenic tri- or penta-chloride, sulphur monochloride, titanium tetrachloride, and boron fluoride; acids such as sulphuric, phosphoric, chlorsulphonic, fluoboric, or formic acid; oxygen; peroxides such as sodium, barium or hydrogen peroxide; percarbonates persulphates, and other persalts; and anhydrides such as acetic, maleic or phthalic anhydride.  Other solvents which may be present are acetic acid; methyl, ethyl, propyl, isopropyl, butyl or isobutyl alcohol; acetone; esters such as methyl, ethyl, propyl or butyl acetate or butyrate; solvent naphtha, benzene and xylene; tetra- and decahydronaphthalene; cyclohexane and methylcyclohexane; cyclohexanol; and saturated hydrocarbons such as pentane, hexane, heptane and octane. Specification 384,654 is referred to.ALSO:Oily products are obtained by polymerizing monovinylacetylene in the absence of other polymerizable substances.  Polymerization may be effected by the action of heat in the presence or absence of air; polymerization catalysts and solvents may be present. Examples 1-11 describe processes in which monovinylacetylene is heated to 80-150 DEG  C. under various conditions to produce non-volatile liquid polymerization products; generally, a partial polymerization is effected, and the unchanged material and volatile products are distilled off at about 100 DEG  C.; in examples 5, 8, and 11 benzoyl peroxide is added as a catalyst; in examples 8 and 11 the process is effected continuously in a heated coil through which the vinylacetylene flows; in examples 6, 7, and 11 toluene is present as a solvent; in examples 9 and 10 manganese dioxide and sodium perborate respectively are added as catalysts; the liquid products are unsaturated and are useful as drying oils for paints or varnishes.  Other catalysts which may be employed are alkali metals, such as lithium, sodium, or potassium; alkaline-earth metals such as calcium or barium; alloys of the said metals, such as the eutectic of sodium and potassium; halides such as aluminium, zinc or cuprous chloride, stannous or stannic chloride, antimony or arsenic tri- or pentachloride, sulphur monochloride, titanium tetrachloride, and boron fluoride; acids such as sulphuric, phosphoric, chlorsulphonic, fluoboric, or formic acid; oxygen; peroxides such as sodium, barium or hydrogen peroxide; percarbonates, persulphates, and other per-salts; and anhydrides such as acetic, maleic, or phthalic anhydride.  Other solvents which may be present are acetic acid; methyl, ethyl, propyl, isopropyl, butyl or isobutyl alcohol; acetone; esters such as methyl, ethyl, propyl or butyl acetate or butyrate; solvent naphtha; benzene and xylene; tetra- and deca-hydronaphthalene; cyclohexane and methylcyclohexane; cyclohexanol; and saturated hydrocarbons such as pentane, hexane, heptane, and octane. Specification 384,654 also is referred to.