Patent GB-611919-A (GB)
Title: A process for the manufacture of valuable reaction products of high-molecular unsaturated substances containing more than one unsaturated grouping in the molecule with inorganic acids or acid anhydrides
IPC: C08C19/00
Filed: 1945-11-30
Abstract: The reaction between polymers of average molecular weight above 5000 and containing a plurality of unsaturated carbon-to-carbon linkages and inorganic acids or acid anhydrides in the presence of aliphatic, cyclic or aliphatic-cyclic ethers is accelerated by first subjecting the mixture of unsaturated substance and ether to a slight oxidation by oxygen or an oxygen-yielding compound. Examples are polymers of dienes and their derivatives, polymers of acetylenes, copolymers of these with each other, copolymers of butadienes with vinyl acetylene, copolymers of dienes or acetylenes with isobutene, styrene, vinyl chloride, vinyl esters, acrylic and methacrylic acids, acrolein, methyl isopropenyl ketone and vinyl ethyl ether.  The inorganic acids or anhydrides are those in which the acid forming elements are not present in their highest valency, e.g. sulphur dioxide, nitrogen trioxide, phosphorus trioxide, the corresponding acids or aqueous solutions, hydrogen sulphide, and hydrochloric and hydrobromic acids. Plasticizers, fillers, stabilizers and colouring matter may also be present.  Examples of ethers are diethyl ether, di-isopropyl ether, pentamethylene oxide and dioxane.  Oxygen-yielding substances include air, ozone, hydrogen peroxide, acetyl, benzoyl and tetrahydronaphthalene peroxides, persulphates, percarbonates and perborates.  The oxidation, which may be effected by adding .1-1 per cent of the oxidizing compound to the polymer dissolved in the ether or in a mixture of the ether and benzene, should only proceed to the formation of peroxide-like compounds without other oxidation and decomposition products being formed. The invention may be applied to the manufacture of products such as filaments, tapes, films and foils when solutions of the high molecular substances are extruded into media, e.g. methyl or ethyl alcohol and greater reaction may be brought about by using mixtures, e.g. natural rubber and polybutadiene.ALSO:The reaction between high molecular unsaturated substances and inorganic acids or acid anhydrides in the presence of aliphatic, cyclic or aliphatic-cyclic ethers is accelerated by first subjecting the mixture of unsaturated substance and ether to a slight oxidation by oxygen or an oxygen-yielding compound.  The high molecular substances include natural rubber and its unsaturated derivatives, polymers of dienes and their derivatives, polymers of acetylenes, copolymers of these with each other, butadienevinyl acetylene copolymers, copolymers of dienes or acetylenes with isobutene, styrene, vinyl chloride, vinyl esters, acrylic and methacrylic acids, acrolein, methyl isopropenyl ketone and vinyl ethyl ether.  Plasticizers, fillers, stabilizers and colouring matter may also be present.  Suitable acids or anhydrides are sulphur dioxide, nitrogen trioxide, phosphorous trioxide, the corresponding acids or aqueous solutions, hydrogen sulphide and halogen hydracids, e.g. HCl and HBr.  Examples of ethers are diethyl ether, diisopropyl ether, pentamethylene oxide and dioxane.  Oxygen-yielding substances include air, ozone, hydrogen peroxide, acetyl, benzoyl and tetrahydronaphthalene peroxides, persulphates, percarbonates and perborates.  The oxidation, which may be effected by adding ,1-1 per cent of the oxidizing compound to the high molecular substance dissolved in the ether or in a mixture of the ether and benzene, should only proceed to the formation of peroxide-like compounds without other oxidation and decomposition products being formed.  The invention may be applied to the manufacture of products such as filaments, tapes, films and foils when solutions of the high molecular substances are extruded into media, e.g. methyl or ethyl alcohol and water, saturated with the acid or anhydride.  Greater reaction is sometimes brought about by using a mixture of two or more of the high molecular substances, e.g. a mixture of natural rubber and polybutadiene.