Patent GB-795370-A (GB)
Title: Production of polymers
IPC: C08F36/04
Filed: 1956-04-18
Abstract: Butadiene or isoprene or a mixture thereof is polymerized in the presence of a catalyst prepared by the interaction of (a) an organic aluminium compound having the general formula R2AlX in which R is an alkyl, cycloalkyl or alkyl group and X is an hydrogen or halogen atom or an alkyl, cycloalkyl or aryl group with (b) a chloride, bromide or iodide of titanium or zirconium. The aluminium compounds may be triethylaluminium, triisobutylaluminium, trioctylaluminium, didodecyloctylaluminium, diisobutylaluminium hydride, tridodecylaluminium, diphenylaluminium bromide, dipropylcyclohexylaluminium, ditolylmethylaluminium, tri - (b  - phenylethyl)aluminium, diethylaluminium chloride, diisobutylaluminium chloride, diisobutylaluminium iodide and di-(b -cyclohexylpropyl)isobutylaluminium.  Preferably the tetra-chlorides and -iodides of titanium and zirconium are employed, the corresponding di- and tri-halides may also be used. Formation of the catalyst may be effected in the presence of a solvent such as liquefied propane, isobutane, normal butane, normal hexane, isomeric hexanes, cyclohexane, methyl cyclopentane, dimethylcyclohexane, dodecane, kerosene, naphtha, benzene, toluene, ethylbenzene, cumene, decalin, ethylene dichloride, chlorobenzene, diethyl ether, odichlorobenzene, dibutyl ether, tetrahydrofurane or dioxane.  From 0.01 to 5 per cent of catalyst based on the monomer may be used; and the monomer may be stirred or bubbled into a liquid suspension of the catalyst.  Catalyst poisons such as oxygen, water, carbon dioxide, carbon monoxide, acetylene and vinyl acetylene should preferably be removed.ALSO:Butadiene or isoprene or a mixture thereof is polymerized in the presence of a catalyst prepared by the interaction of (a) an organic aluminium compound having the general formula R2AlX in which R is an alkyl, cycloalkyl or aryl group and X is an hydrogen or halogen atom, or an alkyl, cycloalkyl or aryl group, with (b) a chloride, bromide or iodide of titanium or zirconium. The monomers may also be admixed with vinyl aromatic hydrocarbons such as styrene or vinyltoluene and also ethylene.  The aluminium compounds may be triethylaluminium, triisobutylaluminium, trioctylaluminium, didodecyloctylaluminium diisobutylaluminium hydride, tridodecylaluminium, diphenylaluminium bromide, dipropylcyclohexylaluminium, ditolylmethylaluminium, tri - (b  - phenylethyl) aluminium, diethylaluminium chloride, diisobutylaluminium chloride, diisobutylaluminium iodide and di(b  - cyclohexylpropyl) isobutylaluminium.  Preferably the tetra-chlorides and -iodides of titanium and zirconium are employed, the corresponding di- and tri-halides may also be used. Formation of the catalyst may be effected in the presence of a solvent such as liquefied propane, isobutane, normal butane, normal hexane, isomeric hexanes, cyclohexane, methyl cyclopentane, dimethylcyclohexane, dodecane, kerosene, naphtha, benzene, toluene, ethylbenzene, cumene, decalin, ethylene dichloride, chlorobenzene, diethyl ether, o-dichlorobenzene, dibutyl ether, tetrahydrofurane or dioxane.  From 0.01 to 5 per cent of catalyst based on the monomer may be used, and the monomer may be stirred or bubbled into a liquid suspension of the catalyst.  Catalyst poisons such as oxygen, water, carbon dioxide, carbon monoxide, acetylene and vinyl acetylene should preferably be removed.  In examples: (1) polybutadiene is obtained by polymerizing butadiene in kerosene in nitrogen in the presence of a catalyst consisting of the reaction product of triethylaluminium and titanium tetrachloride; (2) an ethylene-butadiene copolymer; and (3) a butadiene-styrene copolymer is obtained in a similar fashion.