Patent GB-802510-A (GB)
Title: Improvements in and relating to the polymerisation of acetylenic compounds
Inventor: SMITH WILLIAM ROY
IPC: C08F10/00
Filed: 1955-11-08
Abstract: Tri- and hexa-substituted benzene hydrocarbons are prepared by the polymerization of acetylenes of the formula CR­CR1, where R and R1 are univalent hydrocarbon radicals and R may also be hydrogen, the polymerization being carried out by bringing the acetylene into contact with a catalyst formed by reacting (a) at least one organo compound of at least one nontransition metal of Groups I, II and III of the periodic system with (b) a compound of a transition metal. The component (a) should contain at least one hydrocarbon radical attached to the metal and any remaining valencies may be satisfied with hydrogen or halogen.  Suitable hydrocarbon radicals are alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl; suitable metals are aluminium, beryllium, zinc, magnesium, lithium and sodium. Complete alkyls or alkyl hydrides of aluminium and an alkali metal are also useful.  Specified compounds are aluminium triethyl, sodium aluminium tetrapropyl, lithium aluminium tetraethyl, lithium propyl, sodium phenyl, zinc diethyl, aluminium ethyl dihydride, aluminium diethyl hydride, sodium aluminium tetraphenyl, sodium aluminium triethyl hydride, lithium aluminium propyl trihydride, and potassium aluminium trimethyl fluoride. This component may be used in the form of a complex with ethers, thio-ethers, or amines.  The component (b) may be a halide, oxyhalide, complex halide, freshly precipitated oxide or hydroxide, alcoholate, acetate, benzoate, or acetylacetonate of titanium, zirconium, hafnium, thorium, uranium, vanadium, niobium, tantalum, chromium, manganese, molybdenum or tungsten. Mixtures may be used.  Specified compounds are titanium tetrachloride and tetrafluoride, vanadium tetrachloride, molybdenum pentachloride and tungsten hexachloride.  The components (a) and (b) may be used in a molar ratio between 10:1 and 1:10.  Mono-substituted acetylenes yield 1,2,4- and 1,3,5-tri-substituted benzenes and disubstituted benzenes yield hexasubstituted benzenes.  Typical acetylenes are methyl- or phenyl-acetylene and dimethyl- or diphenyl-acetylene; mixtures of acetylenes may also be used.  Inert solvents for the acetylene may be used such as butanes, pentanes, hexanes, cyclohexane, benzene and toluene.  If the acetylene is a gas under the reaction conditions it may be passed over or bubbled through the catalyst. Temperatures of 50-100 DEG  C. are convenient and atmospheric pressure.  Water and oxygen should be avoided and nitrogen may be used as an inert gas to displace air.  In the examples: (1) methyl acetylene is polymerized to 1,2,4- and 1,3,5-trimethyl benzene in the presence of aluminium triethyl and titanium tetrachloride in methyl cyclohexane; (2) butyne-2 is polymerized to hexamethyl-benzene; (3) diphenyl acetylene is polymerized to hexaphenylbenzene.  The Provisional Specification in addition describes the polymerization of acetylenic compounds CR­CR1, where R and R1 may each be hydrogen, an ester group or a hydrocarbon radical which may be substituted with halogen or ester groups including acetylene and di-p-chlorophenyl acetylene.  The non-transistion metal in the organo-metallic compound may be boron. The use of complex metal alkyls such as sodium aluminium tetraethyl and lithium aluminium tetrapropyl and of hydrides of Group III metals such as aluminium or gallium hydride is also referred to.  A mixture of acetylene and propyne is said to yield benzene, toluene, xylenes and trimethylbenzenes. An additional exxample describes the formation of benzene and solid polymers by polymerization of acetylene in methylcyclohexane with titanium tetrachloride and aluminium triethyl. This additional matter does not appear in the Complete Specification. Specifications 757,524 and 762,200 are referred to.