Patent GB-421146-A (GB)
Title: Improvements in the manufacture and production of artificial masses
IPC: C08F36/16
Filed: 1934-02-28
Abstract: Elastic, ductile products are obtained by polymerizing 1-chlor-butadiene-1 : 3 in the absence of large amounts of oxygen, for example, in presence of nitrogen, hydrogen, or inert gases, at decreased, atmospheric or increased pressure.  The process may be carried out at temperatures of from 0--100 DEG  C., but preferably at 0--50 DEG  C.; accelerating agents such as oxygen, air, alkali metals, their alloys, peroxides such as benzoyl peroxide or hydrogen peroxide, and actinic rays may be employed, or, alternatively, retarding agents such as aromatic hydroxy compounds, or amines, or low temperatures.  Non-polymerizable solvents or diluents such as dimethyl ether, diethyl ether, hydrocarbons, such as benzene, carbon tetrachloride and other chlorinated hydrocarbons, or polymerizable solvents such as butadiene, isoprene, styrene, and methyl-isopropenyl-ketone, or an aqueous medium giving an emulsion may also be employed.  When an emulsion of the 1-chlor-butadiene-1 : 3 is employed, stabilizing agents such as wetting or emulsifying agents may be added, with, if desired, accelerators or retarders and with natural latex or other emulsions.  The products may be obtained soluble, insoluble or capable of swelling, in organic solvents and may be obtained mixed with fillers, acid binding agents, softening agents, vulcanization accelerators, anti-agers, dyes, or sulphur, added during, before, or after the polymerization.  The products may be used as solutions, pastes or emulsions, for impregnating, as coating materials, packings, putties, and as solids, for motor car tyres, conveying bands, packings stable to oil and like technical rubber articles. According to examples, 1 - chlor - butadiene-1 : 3 is polymerized, (1) by heating in a vacuum at 30 DEG  C. and the product worked up with aldol-a -naphthylamine into a sheet; (2) by heating at 25 DEG  C. with benzoyl peroxide and toluene, the product being worked up for a coating-mass or by vulcanization; (3) by heating in vacuo with benzoyl peroxide at 60 DEG  C. to give an elastic product suitable for rolling; (4) by warming with sodium at 30 DEG  C. in presence of a small quantity of air, to give a product suitable for rolling; (5) by warming with methylheptane and sodium wire in presence of a small quantity of air to give a product insoluble in benzene suitable for rolling; (6) by forming an emulsion with sodium oleate solution, and coagulating with acetic acid, the product being worked up to an elastic sheet with aldol-a -naphthylamine, or mixed with carbon black, dicyclohexyl-aminedithiocarbamic dicyclohexylamine, colophony, and the rubber softening agent known under the Registered Trade Mark " Kautschol," and vulcanized without or with sulphur to give strong elastic products; (7) by heating as an emulsion with methyl isopropenyl ketone water, ammonia, oleic acid and hydrogen peroxide, at 30 DEG  C. and coagulating with acetic acid; (8) by emulsifying with butadiene, sodium oleate solution, and magnesium oleate, in presence of air and warming at 60 DEG  C., followed by treating with acetic acid.ALSO:Elastic, ductile products are obtained by polymerizing 1-chlor-butadiene-1 : 3 in the absence of large amounts of oxygen, for example in presence of nitrogen, hydrogen, or inert gases, at decreased, atmospheric or increased pressure.  The process may be carried out at temperatures of from 0-100 DEG  C., but preferably at 0-50 DEG  C.; accelerating agents such as oxygen, air, alkali metals, their alloys, peroxides such as benzoyl peroxide or hydrogen peroxide, and actinic rays may be employed, or alternatively, agents such as aromatic hydroxy compounds, or amines, or low temperatures.  Non-polymerizable solvents or diluents such as dimethyl ether, diethyl ether, hydrocarbons, such as benzene, carbon tetrachloride and other chlorinated hydrocarbons or polymerizable solvents such as butadiene, isoprene, styrene and methylisopropenyl-ketone, or an aqueous medium giving an emulsion may also be employed.  When an emulsion of the 1-chlor-butadiene-1 : 3 is employed, stabilizing agents such as wetting or emulsifying agents may be added, with, if desired, accelerators, or retarders and with, for example, natural latex or other emulsions.  The products may be obtained soluble, insoluble or capable of swelling, in organic solvents, and may be obtained mixed with fillers, acid binding agents, softening agents, vulcanization accelerators, anti-agers, dyes, or sulphur, added during, before, or after the polymerization. The products may be used as solutions, pastes or emulsions, for impregnating, as coating materials, packings, putties, and as solids, for motor car tyres, conveying bands, packings stable to oil and like technical rubber articles.  According to examples, 1-chlor-butadiene-1 : 3 is polymerized (1) by heating in a vacuum at 30 DEG  C. and the product worked up with aldol-a -naphthylamine into a sheet; (2) by heating at 25 DEG  C. with benzoyl peroxide and toluene, the product being worked up for a coating-mass or by vulcanization; (3) by heating in vacuo with benzoyl peroxide at 60 DEG  C. to give an elastic product suitable for rolling; (4) by warming with sodium at 30 DEG  C. in presence of a small quantity of air, to give a product suitable for rolling; (5) by warming with methylheptane and sodium wire in presence of a small quantity of air to give a product insoluble in benzene suitable for rolling; (6) by forming an emulsion with sodium oleate solution, and coagulating with acetic acid, the product being worked up to an elastic sheet with aldol-a -naphthylamine, or mixed with carbon black, dicyclohexylaminedithiocarbamic dicyclohexylamine, colophony, and the rubber-softening agent known under the Registered Trade Mark "Kautschol," and vulcanized without or with sulphur to give strong elastic products; (7) by heating as an emulsion with methyl isopropenyl ketone, water, ammonia, oleic acid and hydrogen peroxide, at 30 DEG  C. and coagulating with acetic acid; (8) by emulsifying with butadiene, sodium oleate solution and magnesium oleate, in presence of air and warming at 60 DEG  C., followed by treating with acetic acid.