Patent GB-969074-A (GB)
Title: Polymerization catalyst
IPC: C08F4/06
Filed: 1962-06-18
Abstract: Polymers and copolymers are formed from ethylenically unsaturated monomers using as catalyst a mixture of (A) a strong reducing agent, (B) a compound of a heavy metal, boron, silicon, arsenic or tellurium and (C) a hydrocarbonaminated silicon compound or titanium compound or mixture of the two, in which compounds alkyl amino groups are attached directly to atoms of silicon or titanium by means of a silicon- or titanium-nitrogen bond. Reducing agents (A) listed are metals such as zinc, aluminium, magnesium, tin, lithium, sodium and potassium; organometallic compounds of metals of Group IA, IIA, IIB, IIIA, IVA and boron (Lange's Periodic Table)e.g. butyl lithium, phenyl sodium, phenyl potassium, diethyl magnesium, triethyl aluminium, diethyl zinc, diethyl cadmium, tetraethyl tin, tetraphenyl lead, triethyl boron, ethyl magnesium chloride, diethyl aluminium chloride (many others are listed); phosphides and nitrides of the above metals; partially hydrogenated aromatic compounds such as tetratin and dihydronaphthalene; pentahydrocarbon nitrogen, phosphorus, arsenic and antimony compounds having one of the following formulae (i) R1R2R3R4R5y, (ii) R1R2R3R4y) +(R5)-, (iii) (R1R2R4y-)\sB(-R3,5)-, (iv) R1R2-R4y=R3,5 where y is nitrogen, phosphorus, arsenic or antimony; R1, R2, R3, R4, R5 are hydrocarbon groups of 1 to 30 carbon atoms, any pair of which may constitute a single hydrocarbon radical twice bonded to y; lists of these compounds are given including benzyl tetramethyl ammonium and 9-fluorenyl tetraphenyl phosphonium.  The compounds (B) may be the oxides, bromides, chlorides, iodides, acetylacetonates and alkoxides of boron, silicon, arsenic, tellurium, or metals of Group IB to VIIB, VIIIA, IIIA to VIA plus lutetium but not including C, Si, N, P, As, O, S, Se and Te. Lists of compounds are given but a preferred one is obtained by heating metallic aluminium with titanium tetrachloride to produce Ti3AlCl12 which may be "activated" by grinding. Compounds (C) specified are tetrakis-(dihydrocarbonamino) silanes and titanium of the formula <FORM:0969074/C3/1> hexakis siloxanes and "z" is a silicon or titanium atom.  The corresponding titanium compounds of the formula: <FORM:0969074/C3/2> and compounds having the formula: <FORM:0969074/C3/3> and alkylamino silicone polymers.  Lists of actual compounds are given including tetrakis-(diethylamino) titanium and tri-(dimethylamino) ethyl silane.  Many monomers are listed e.g. olefines, styrene and substituted styrenes, vinyl naphthalene, butadiene and related compounds, vinyl and vinylidene monomers including vinyl chloride, trifluorochloroethylene, alkyl acrylates and methacrylates, acrylonitrile and methacrylonitrile, vinyl acetate and propionate, vinylpyridine and carbazole.  The catalysts are prepared by mixing the components together preferably in a hydrocarbon vehicle; other materials may be added to the catalyst e.g. hexamethyl phosphoramide, and the polymerization is preferably carried out in a saturated liquid hydrocarbon, the products being purified for example by washing with alcohols, acids and ammonia &c. In the examples propylene is polymerized, the solvent is heptane and the catalyst is (a) sodium phenyl suspension + hexakis -(dimethylamino) siloxane +Ti3AlCl12 suspension or (b) sodium phenyl suspension +Ti3AlCl12 +tetrakis -(dimethylamino) silane or (c) metallic sodium suspension + tetrakis (dimethylamino) silane + Ti3AlCl12 or (d) sodium phenyl suspension + tetrakis -(dimethylamino) titanium + tetrakis -(dimethylamino) silane + Ti3AlCl12.