Patent GB-444260-A (GB)
Title: Improvements in the manufacture and production of polymerised vinyl compounds
IPC: C08F2/18
Filed: 1934-09-22
Abstract: Resins are obtained by polymerizing N-vinyl pyrrole or N-vinyl compounds containing the pyrrole ring with or without another polymerizable vinyl compound.  Pyrrole derivatives specified are N-vinylcarbazole, N-vinyltetrahydrocarbazole, N - vinylisopropylcarbazole, N - vinylindole, and N - vinylnaphthocarbazole, which can be prepared as described in Specification 438,281.  Polymerization is effected by heating the pyrrole compound alone or in solution, emulsion or suspension, and with or without accelerators or retarders, and it may be accelerated by light.  Accelerators specified are agents having an acid action such as boron or its addition compound with dibutyl ether, tin tetrachloride, zinc chloride, aluminium chloride, sulphur dioxide, carbon dioxide, halogen, halogen hydrides, sulphuric acid, and acid chlorides, e.g. phosgene, sulphuryl-, thionyl-, acetyl-, benzoylchlorides; atmospheric oxygen, ozone, and inorganic or organic compounds capable of supplying oxygen, e.g. hydrogen-, sodium-, barium-, and benzoylperoxide and sodium and other persulphates perborates, chromates, chlorates, perchlorates and nitrates having weaker oxidizing action than permanganates, e.g. sodium and potassium chromates; and sulphur compounds, e.g. carbon bisulphide, thiophenol, thiocresol; surface agents such as active carbon and bleaching earths.  Retarders specified are alkali or alkaline earth metals and their oxides, hydroxides, and carbonates, acetates, phosphates and formates, e.g. metallic sodium, potassium and calcium, sodium and potassium hydroxides, monohydric and polyhydric alcohols, e.g. ethylene glycol, glycerine; dioxane, dibenzyl ether; heavy metals and their salts, e.g. copper salts especially oil-soluble salts such as the stearate; aromatic hydroxyl compounds; and ammonia and organic bases, e.g. aniline, pyridine, piperidine.  Neutral salts may be added before polymerization, e.g. sodium, and calcium chlorides, Glauber's salt.  Solvents specified for use in the polymerization are ligroin, cyclohexane, benzene, toluene, glacial acetic acid, a mixture of toluene and xylene, and trichlorethylene.  Substances specified for obtaining mixed polymers with the pyrrole compounds are vinyl ethers, esters and chloride, e.g. ethylene glycol vinyl phenyl ether; styrene; acrylic acid and its esters and nitrile; isopropenyl methyl ketone and other unsaturated ketones; unsaturated hydrocarbons, e.g. butadiene, isoprene, and vinyl acetylene; and polymerizable oils, e.g. linseed and wood oils. These substances may be polymerized with the pyrrole compounds, or their polymers (including polymethacrylic esters, and mixed polymers of some of the specified substances) may be added.  The products may be treated with chlorine or other halogen.  Fillers, dyestuffs, pigments, and softeners may be added during or after polymerization.  Fillers specified are wood flour, cellulose and wood fibres, carbon black, graphite, asbestos, talc, quartz, heavy spar, zinc oxide, titanium oxide.  Softeners specified are tricresyl phosphate, dibutyl phthalate, polybenzyl naphthalene, polyglycols and their derivatives; chlorinated polynuclear hydrocarbons, such as naphthalene, acenaphthene, and diphenyl; paraffin wax, natural and synthetic waxes, e.g. Carnauba wax; polymers of low molecular weight containing from 2 to 4 molecular proportions of N-vinyl pyrrole, obtained by polymerizing with a mineral acid other than sulphuric acid as catalyst, e.g. with hydrochlorine acid.  The products may be used in making plastic masses, coatings, lacquers, priming compositions, electric insulation materials, artificial leather, and oilcloth; binding agents for abrasive papers, emery wheels, and brake liners; in making threads, films, foils, ribbons, tubes and rods, by extending the heated material; in making films by pouring a solution; in making boxes, buttons, buckles, handles, ornaments, cups, insulating ribbon, condenser foil, switches, valve sockets, and bobbins; and in coating metals and other materials by injection moulding, casting, and pressing.  The material may be shaped by rolling, pressing, casting, injection moulding, cutting, sawing, turning, boring, filing, and polishing.  In examples 1 to 20, N-vinyl carbazole is polymerized with sodium, ethylene glycol, sodium hydroxide, concentrated sulphuric acid, hydrogen chloride with or without nitrogen as diluent, gaseous boron fluoride, hydrogen peroxide, the addition compound of dibutyl ether and boron fluoride, sodium peroxide, benzoyl peroxide, sodium persulphate, potassium chromate or sodium chromate, or by heating without an accelerator; the vinyl compound is treated alone, (examples 1-3, 5); in the presence of solvents, (examples 4, 6--9, 11, 12); in emulsion with sodium butylnaphthalene sulphonate, turkey red oil, and ammonia, (example 10); or in the presence of aqueous alkalies, (examples 13--20); and in example 11, the N-vinyl carbazole is polymerized together with ethylene glycol vinyl phenyl ether, obtainable as described in Specification 369,297.  In further examples, (21) N-vinyl-isopropylcarbazole is polymerized with benzoyl peroxide; (22) N-vinylindole with the addition compound of boron fluoride and dibutyl ether; and (23) N-vinyltetrahydrocarbazole by heat.  Polymers of N-vinylpyrrole containing 2 to 4 molecular proportions are obtained as described above.