Patent GB-806095-A (GB)
Title: Improvements in or relating to polymeric materials
IPC: C08F220/44
Filed: 1956-08-14
Abstract: Copolymers of 3-methylene-1-cyclobutene and an ethylenically unsaturated monomer, preferably with at least one terminal methylene group, which contain from 1 to 45 per cent by weight of polymerized methylenecyclobutene, are obtained by addition and have at least one of the annular carbons of each four-carbon ring in the main chain of atoms in the polymer structure.  Ethylene, propylene, butylene, butadiene, isoprene, vinyl fluoride and vinylidene chloride, vinyl benzoate, acetate and laurate, ethyl vinyl, and methyl isopropenyl ketones, ethyl acrylate, methyl methacrylate, methacrylonitrile and methacrylic acid, maleic and fumaric acids, their esters, nitriles and anhydrides, tri - tetra - fluoroethylenes, chlorotrifluoroethylene, styrene and a -methyl styrene may be the monomers and emulsion, lead, bulk and solution copolymerization methods, with initiators such as di-t-butyl, di-ethyl, diacetyl, dibenzoyl, dilauroyl peronides, t-butylhydroperonides, peracetic, perbenzoic, perphthalic acids, ammonium and sodium persulphates, a ,a 1 - azodiiso butyronitrile, 1,11-azodicylohexone - carbonitrile, dimethyl - a ,a 1-azodisobutyrate, a ,a 1 - azodiisobutyramide, and a - (carbamylazo) - isobutyronitrile, condensation products of aluminium trialkyls with titanium, vanadium or zirconium tetrachloride, e.g. the condensation product of lithium aluminium tetra-n-decyl with titanium tetrachloride, alkyl magnesium halides, sodium and potassium amides, boron trifluorides and aluminium trichloride may be used.  In examples, 3 - methylene - 1 - cyclobutene is copolymerized with styrene by agitation at 40 DEG  C. in water containing sodium lauryl sulphate, ammonium persulphate, and sodium bisulphite, the product coagulated in saturated sodium chloride solution and purified by precipitation from a benzene solution with methanol; with n-butylmethacrylate by agitation as above, in water containing sodium lauryl sulphate, ammonium persulphate and sodium bisulphite, and the product co-agulated in absolute methanol containing hydroquinone and concentrated hydrochloric acid; with acrylonitrile by agitation with water containing sodium lauryl sulphonate, ammonium persulphate and sodium bisulphite, precipitated in absolute methanol, to a gel soluble in dimethyl-formamide from a solution in which it may be precipitated in water.  The copolymers may be cross-linked by further heating at from 190 DEG  to 225 DEG  C. to give a benzene insoluble product.  A copolymer with ethylene may be prepared by introducing gaseous ethylene to a mixture of a solution of lithium aluminium tetradecyl in pure, dry, cyclohexane and titanium tetrachloride in cyclohexane which is heated to 80 DEG  C. and a solution of 3-methylene-1-cyclobutene in cyclohexane added dropwise.  The catalyst is destroyed with methanol, the product precipitated by adding the mixture to methanol, washed and dried.  The copolymers may be cross-linked by heat treatment at from 100 DEG  to 325 DEG  C. Shaped objects, printing inks, laminates, fibres, and coating compositions applied from solution in benzene for example, which may contain pigments such as titanium dioxide may be set to form insoluble products.  Specification 805,664 is referred to.ALSO:Methylenecyclobutene is prepared by reacting methyl 3-methylenecyclobutane-1-carbonylate with hydrazine hydrate, treating the hydrazide formed with sodium nitrite in aqueous hydrogen chloride and diethyl ether to give 3-methylenecyclobutane - 1 - carbonyl azide, which is refluxed in methanol to form methyl-N-(3-methylenecyclobutyl) urethane, which is treated with sodium hydroxide to give 3-methylenecyclobutylamine, converted to quaternary ammonium salt with methyl iodide in the presence of sodium carbonate, and finally treated with 40 per cent aqueous sodium hydroxide at 120 DEG  to 140 DEG  C.  Specification 805,664 is referred to.