Patent GB-365102-A (GB)
Title: Improvements in the conversion of organic compounds into compounds of higher molecular weight
IPC: C08F2/02
Filed: 1930-07-07
Abstract: Organic substances are polymerized, with or without heat and catalysts, at pressures of 2000 atmospheres or more, 25000 atmospheres being mentioned.  The organic compounds may be used alone, or in the form of mixtures, solutions, or emulsions.  Any suitable method of applying the pressure may be used; in the method described, the material is placed in a small glass tube in a steel container with its open end under mercury, the whole being then placed in the pressure apparatus, which comprises a hydraulic pump delivering 1000 atmospheres, a hydraulic intensifier giving a ratio of increase of 25 : 1, and a high-pressure vessel consisting of a heat-treated block of chrome vanadium steel 6 inches in diameter with a 1-inch hole drilled in it to form the reaction chamber; suitable joints are described in proceedings of the American Academy, February, 1914, which also describes the whole apparatus.  The pressure is transmitted to the mercury through kerosene.  The examples describe the treatment of (1) isoprene which has been exposed to air, the pressures being from 5000 to 12000 atmospheres; (2) 2:3 dimethyl butadiene at 10000 atmospheres; (3) styrene and indene at 12000 atmospheres; (4) and (5) vinyl acetate and bromide at 11400 atmospheres; (6) isoprene and petroleum ether at 12000 atmospheres; (7) a mixture of styrene and malonic ester at 12000 atmospheres; (8) a mixture of vinyl bromide and acetate at 12000 atmospheres; (9) isoprene (sealed out of contact with air) at 12000 atmospheres; (10) n-butyraldehyde at 11200 atmospheres, the product being hard and brittle, melting at 115-120 DEG  C., but slowly reverting to the original form on standing; (11) isobutyraldehyde at 12000 atmospheres, yielding a solid polymerizate smelling of the original compound and slowly reverting to it on standing; (12) isoprene with benzoyl peroxide at 12000 atmospheres; (13) isoprene alone, isoprene with benzoyl peroxide, and isoprene with benzaldehyde which has been exposed to the air and therefore contained benzoyl peroxide, the reaction being effected in each case at 2000 atmospheres and 80 DEG  C. for 7 hours, the proportions polymerized being 9, 32, and 22 per cent respectively.  Other compounds which may be polymerized include aliphatic hydrocarbons containing two or more conjugated double bonds, esters of unsaturated alcohols, unsaturated halides, unsaturated aldehydes, and aromatic compounds with unsaturated side-chains such as styrene and indene.ALSO:Caoutchouc, synthetic; polymerized vinyl esters, styrene with malonic ester, and aldehydes.--Organic substances are polymerized, with or without heat and catalysts, at pressures of 2000 atmospheres or more, 25000 atmospheres being mentioned.  The organic compounds may be used alone, or in the form of mixtures, solutions or emulsions.  Any suitable method of applying the pressure may be used; in the method described, the material is placed in a small glass tube in a steel container with its open end under mercury, the whole being then placed in the pressure apparatus, which comprises a hydraulic pump delivering 1000 atmospheres, a hydraulic intensifier giving a ratio of increase of 25 : 1, and a high pressure vessel consisting of a heat-treated block of chrome vanadium steel 6 in. in diameter with a one-inch hole drilled in it to form the reaction chamber; suitable joints are described in Proceedings of the American Academy, February 1914, which also describes the whole apparatus.  The pressure is transmitted to the mercury through kerosene.  The examples describe the treatment of (1) isoprene which has been exposed to air, the pressures being from 5000 to 12000 atmospheres; (2) 2,3-dimethyl butadiene at 10000 atmospheres; (3) styrene and indene at 12000 atmospheres; (4) and (5) vinyl acetate and bromide at 11400 atmospheres; (6) isoprene and petroleum ether at 12000 atmospheres; (9) a mixture of styrene and malonic ester at 12000 atmospheres; (8) a mixture of vinyl bromide and acetate at 12000 atmospheres; (9) isoprene (sealed out of contact with air) at 12000 atmospheres; (10) n-butyraldehyde at 11200 atmospheres, the product being hard and brittle, melting at 115-120 DEG  C., but slowly reverting to the original form on standing; (11) isobutyraldehyde at 12000 atmospheres, yielding a solid polymerizate smelling of the original compound and slowly reverting to it on standing; (12) isoprene with benzoyl peroxide at 12000 atmospheres; (13) isoprene alone, isoprene with benzoyl peroxide, and isoprene with benzaldehyde which has been exposed to the air and therefore contains benzoyl peroxide, the reaction being effected in each case at 2000 atmospheres and 80 DEG C. for 7 hours, the proportions polymerized being 9, 32, and 22 per cent respectively.  Other compounds which may be polymerized include aliphatic hydrocarbons containing two or more conjugated double bonds, esters of unsaturated alcohols, unsaturated halides, unsaturated aldehydes, and aromatic compounds with unsaturated side-chains, such as styrene and indene.