Patent GB-340004-A (GB)
Title: Improvements in the polymerisation of unsaturated organic compounds
IPC: C09F9/00
Filed: 1929-08-12
Abstract: Unsaturated organic compounds, such as fatty acids, e.g acrylic, linoleic, ricinoleic and other long chain acids, or their derivatives such as their esters or mixtures of the same e.g. crude linseed oil, unsaturated aliphatic hydrocarbons with more than one double linkage, such as butadiene, isoprene or other diolefines, or mixtures thereof, or unsaturated aromatic compounds such as styrene, are polymerized in the presence of one or more carbonyls of the heavy metals especially of iron, nickel and cobalt, and also of molybdenum, tungsten and chromium, with heating if desired.  The carbonyls, in the proportion of about 0,1 to 10 per cent of the material to be polymerized, are added to such material, in which they usually dissolve, and the mixture warmed.  The efficiency is not impaired if the carbonyls have suffered partial decomposition by the action of light, warm weather, reduced pressure applied during the process, or chemically active, e.g. basic, substances.  Partially polymerized products, e.g. of butadiene, isoprene and like diolefines, or mixtures thereof, produced in known manner, may be converted into elastic, solid products by the process.  Both polymerizations may take place in presence of organic solvents such as aromatic hydrocarbons, or petroleum fractions, esters or ketones, carbon tetrachloride, or mixtures of these with alcohols and like solvents employed in the lacquer industries, especially in the polymerization of very viscous polymerizates or of solid elastic polymerizates to give hard, unelastic products.  Polymerization of partially polymerized diolefines may be effected in the presence of oxygen or oxygen-containing mixtures or agents supplying the same, such as peroxides and ozonides, and of oxygen transferrers such as heavy metal salts of fatty acids of high molecular weight, or of resinic or naphthenic acids, or of organic sulphonic acids, such as polynuclear aromatic sulphonic acids e.g. naphthalene sulphonic acids which may have alkyl or aralkyl radicles such as propyl, butyl or benzyl in the nucleus, sulphonic acids of phenols, naphthols, halogenated hydrocarbons or nitrogenous bases, e.g. aniline, naphthylamine, or pyridines, or from coal tar or mineral oils, or of aliphatic compounds such as can be obtained from paraffin oil, or vegetable oils or fats or their acids, or mixtures of such sulphonic acids. The process may be used in the manufacture of coatings, films, discs, threads and the like or in joining materials with partially polymerized butadienes.  Solid or dissolved sulphur may be added.  In examples, linseed oil is heated with iron or cobalt carbonyl at 300 DEG  C. while passing carbon dioxide, to obtain viscous or solid products; isoprene is warmed with iron carbonyl, while passing air, to give a viscous product which can be worked to rubber-like artlcles; and oily polymerizates of butadiene after addition of iron carbonyl, which may be mixed with sulphur chloride or sulphur in carbon disulphide, or of nickel carbonyl mixed with the chromium salt of a propyl naphthalene sulphonic acid, are painted on to a substratum and dry rapidly, especially on heating to about 95 DEG  C. to give firm coatings.  Specification 328,908 [Class 95, Paints &c.] is referred to.ALSO:Synthetic caoutchouc and other polymerized hydrocarbons; polymerized esters and other derivatives of unsaturated fatty acids.-Unsaturated organic compounds, such as fatty acids, e.g. acrylic, linoleic, ricinoleic and other long chain acids, or their derivatives such as their esters or mixtures of the same e.g. crude linseed oil, unsaturated aliphatic hydrocarbons with more than one double linkage, such as butadiene, isoprene or other diolefines, or mixtures thereof, or unsaturated aromatic compounds such as styrene, are polymerized in the presence of one or more carbonyls of the heavy metals especially of iron, nickel and cobalt, and also of molybdenum, tungsten and chromium, with heating if desired.  The carbonyls, in the proportion of about 0,1 to 10 per cent, of the material to be polymerized, are added to such material, in which they usually dissolve, and the mixture warmed.  The efficiency is not impaired if the carbonyls have suffered partial decomposition by the action of light, warm weather, reduced pressure applied during the process, or chemically active, e.g. basic, substances.  Partially polymerized products, e.g. of butadiene, isoprene and like diolefines, or mixtures thereof, produced in known manner, may be converted into elastic, solid products by the process.  Both polymerizations may take place in presence of organic solvents such as aromatic hydrocarbons, or petroleum fractions, esters or ketones, carbon tetrachloride, or mixtures of these with alcohols and like solvents employed in the lacquer industries, especially in the polymerization of very viscous polymerizates or of solid elastic polymerizates to give hard, unelastic products.  Polymerization of partially polymerized diolefines may be effected in the presence of oxygen or oxygen containing mixtures or agents supplying the same, such as peroxides and ozonides, and of oxygen transferrers, such as heavy metal salts of fatty acids of high molecular weight, or of resinic or naphthenic acids, or of organic sulphonic acids, such as polynuclear aromatic sulphonic acids e.g. naphthalene sulphonic acids which may have alkyl or aralkyl radicles such as propyl, butyl or benzyl in the nucleus, sulphonic acids of phenols, naphthols, halogenated hydrocarbons or nitrogenous bases, e.g. aniline, naphthylamine, or pyridines, or from coal tar or mineral oils, or of aliphatic compounds such as can be obtained from paraffin oil, or vegetable oils or fats or their acids, or mixtures of such sulphonic acids. The process may be used in the manufacture of coatings, films, discs, threads and the like or in joining materials with partially polymerized butadienes.  Solid or dissolved sulphur may be added.  In examples, linseed oil is heated with iron or cobalt carbonyl at 300 DEG  C. while passing carbon dioxide, to obtain viscous or solid products; isoprene is warmed with iron carbonyl, while passing air, to give a viscous product which can be worked to rubber-like articles; and oily polymerizates of butadiene after addition of iron carbonyl, which may be mixed with sulphur chloride or sulphur in carbon disulphide, or of nickel carbonyl mixed with the chromium salt of a propyl naphthalene sulphonic acid, are painted on to a substratum and dry rapidly, especially on heating to about 95 DEG C., to give firm coatings.  Specification 328,908, [Class 2 (iii), Dyes &c.], is referred to.ALSO:Partially polymerized butadienes are used as adhesives and are further polymerized, after the articles to be united have been cemented together, in the presence of one or more carbonyls of the heavy metals especially of iron, nickel and cobalt, and also of molybdenum, tungsten and chromium, with heating if desired.  The carbonyls, in the proportion of about 0,1 to 10 per cent of the material to be polymerized are added to such material in which they usually dissolve, and the mixture warmed.  The efficiency is not impaired if the carbonyls have suffered partial decomposition by the action of light, warm weather, reduced pressure applied during the process, or chemically active e.g. basic, substances. Both polymerizations may take place in presence of organic solvents such as aromatic hydrocarbons, or petroleum fractions, esters or ketones, carbon tetrachloride, or mixtures of these with alcohols and like solvents employed in the lacquer industries, especially in the polymerization of very viscous polymerizates or of solid elastic polymerizates to give hard, unelastic products. Polymerization of partially polymerized diolefines may be effected in the presence of oxygen or oxygen containing mixtures or agents supplying the same, such as peroxides and ozonides, and of oxygen transferrers such as heavy metal salts of fatty acids of high molecular weight, or of resinic or naphthenic acids, or of organic sulphonic acids, such as polynuclear aromatic sulphonic acids e.g. naphthalene sulphonic acids which may have alkyl or aralkyl radicles such as propyl, butyl or benzyl in the nucleus, sulphonic acids of phenols, naphthols, halogenated hydrocarbons or nitrogenous bases, e.g. aniline, naphthylamine, or pyridines, or from coal tar or mineral oils, or of aliphatic compounds such as can be obtained from paraffin oil, or vegetable oils or fats or their acids, or mixtures of such sulphonic acids.  Solid or dissolved sulphur may be added.  Specification 328,908, [Class 121, Starch &c.], is referred to.