Patent GB-831350-A (GB)
Title: Improvements in the production of cyclopolyolefines
IPC: C07C2/48
Filed: 1957-06-04
Abstract: Catalysts for polymerizing acetylenes to cyclopolyolefines comprise (a) a nickel compound, (b) either the product of treating a solution of a Group III metal compound in an organic solvent with an acetylene containing a -C­CH group at 90-180 DEG  C. or the product of the reaction between a compound of aluminium or thallium and a metal derivative of an acetylene containing a -C­CH group and, optionally (c) a compound of an element of Group IVa, IVb or Vb.  The compound (a) may be nickel cyanide, thiocyanate, acetylacetonate aceto-acetic ester or amide or pivalate used in solution in amounts of 0.3 to 2% of the solvent, which may be the same as used in (b), or is alternatively supported on silica gel, alumina, activated charcoal, pumice or fuller's earth.  The product (b) is formed in solution, e.g. in tetrahydrofuran, dioxane or benzene.  In the first alternative the compound is preferably an aluminium or thallium alcoholate or enolate or an alanate or alane, e.g. aluminium ethylate, isopropylate, secondary butylate, acetoacetic ester or acetylacetonate, thallium acetylacetonate, lithium-, sodium- or calciumalanate, ethoxy ethyl chloralane or ethoxy ethyl ethinyl alane in amounts of 0.05-2.5% of the solution.  In the second alternative the halide of aluminium or thallium is preferred.  The compound (c) may be a tetra-alkyl or aryl silane, a dialkyldimercaptoalkyl silane, an ester of orthotitanic acid with a C1-C12 alcohol, a tetraalkyl-, tetraaryl-, trialkylmercaptoalkyl-, dialkyldimercaptoalkyl-, dialkyldimercaptoaryl-, dialkyldimercaptoacyl-, or dialkyldithiocyanogen-stannane, an ester of a di- or tri-alkoxy stannane, a dialkylstannane sulphide, a bis-(trialkylstannane) oxide or an organic compound of nitrogen, phosphorus, arsenic or antimony, including lactams, tertiary amides, open chain amides, trialkyl- and trial-phosphine sulphides and esters of thiophosphoric acid and tetrathiophosphoric acid.  Specification 706,629 is referred to.ALSO:In the preparation of cyclopolyolefines, particularly cyclo-octatetraene, by the cyclizing polymerization of acetylene or its derivatives, containing a -C ­ CH grouping, a solution of a compound of a Group III element in an organic solvent is pretreated with acetylene or a derivative thereof containing a -C ­ CH grouping, either of which may be mixed with an inert gas, at normal or increased pressure and 90-180 DEG  C., or a compound of aluminium or thallium is pretreated with a metal compound of acetylene or a derivative thereof to form an activating solution, to this activating solution is added the nickel compound catalyst and acetylene or a derivative, which may be mixed with an inert gas, is led in at normal or increased pressure and 30-120 DEG  C. The nickel catalyst is conventional and may be the cyanide, thiocyanate, the complex of an enolizable beta-dicarbonyl compound such as acetylcetone and acetoacetic acid esters or amide, or nickel salts of weak organic acids such as the pivalate; they are used in solution in amounts of 0.3 to 2% by weight of the solvent used.  Alternatively the catalyst may be supported on a carrier such as silica gel, alumina, activated charcoal, pumice or fuller's earth as a fixed or fluidized bed in the solvent.  The solvent is preferably one with a high solvent power for acetylene particularly tetrahydrofurane, dioxane or benzene.  The compound of the Group III element may be one derived from a weak acid such as aluminium or thallium alcoholates and enolates, and also olanates and olanes and their derivatives may be used.  Examples are aluminium ethylate, isopropylate, secondary butylate, acetoacetic ester enolate and acetylacetonate, thallium acetylacetonate, lithium-, sodium- and calcium-olanates, ethoxy ethyl chloralane or ethoxy ethyl ethinyl alane.  The compounds are pretreated in solutions of 0.05 to 2.5% strength.  Where an aluminium or thallium compound is treated with a metal compound of acetylene or derivative thereof the compound is preferably a halide.  There may also be added to the nickel catalyst a compound of an element of Group IV such as organic silicon compounds for example tetra-alkyl or tetra-aryl silanes and dialkyldimercaptoalkyl silanes, esters of orthotitanic acid with alkanols of 1 to 12 carbon atoms, organo tin compounds for example tetra-alkyl-, tetra-aryl-, trialkylmercaptoalkyl -, dialkyldimercaptoalkyl -, dialkyldimercaptoaryl -, dialkyldimercaptoacyland dialkyldithiocyanogen-stannanes, esters of di- and tri-alkoxystannanes, dialkylstannane sulphide and bis-(trialkylstannane) oxide; and also compounds of Group V elements such as organic derivatives of nitrogen, phosphorus, arsenic and antimony for example lactams, tertiary amides, open-chain amides, trialkyland triaryl-phosphine sulphides, esters of thiophosphoric acid and tetrathiophosphoric acid.  The process may be carried out continuously or as a batch process and the catalyst and activating solutions may be supplied to the reaction zone separately or together.  The acetylene either for the pretreatment of the activator or for the reaction may be mixed with nitrogen, propane or methane or as an unpurified gas from an electric are preparation, or pure acetylene may be used; it is preferably dried.  Pressures up to 300 atmospheres may be used in either operation.  Specification 706,629 is referred to.