Patent GB-384639-A (GB)
Title: Improvements in or relating to the polymerization of vinyl compounds
IPC: C08F12/08
Filed: 1931-03-02
Abstract: In the polymerization of vinyl compounds the amount of acid present initially together with that produced during polymerization is regulated to be greater than 0 per cent but not substantially greater than the equivalent of 1 per cent of hydrochloric acid, whereby polymers of good colour and low viscosity and of consistently uniform quality are obtained.  This may be achieved, for example, by the addition of mild inorganic bases (such as sodium carbonate), amines (such as diphenylamine, triethanolamine, or pyridine), butyl alcohol, lead tetraalkyls, lead trialkyl chlorides, dioxane, and especially ethylene oxide and similar substances.  The regulation of the acidity enables the reaction to be carried out at higher temperatures, e.g. up to about 150 DEG  C.  If the raw materials contain too little acid, sufficient acid is added to bring the amount up to the ideal. When working above 130 DEG  C. it is usually unnecessary to add acid and advisable to add ethylene oxide owing to the generation of acid during the polymerization.  Where one quantity of vinyl compound has a low acid content and another a high acid content, good results may be obtained by mixing them in suitable proportions.  The process is applicable to the polymerization of mixtures of vinyl compounds, and to the polymerization of polymerizable compositions in the presence of other materials. The polymerization may be carried out by the batch method or by a continuous flow process.  In examples: (1) a mixture of vinyl chloride containing acid as impurity, toluene, and benzoyl peroxide, with, and, for purposes of comparison, without the addition of ethylene oxide, is passed under pressure through a lead-lined tube at 120-125 DEG  C.; (2) a solution in toluene of vinyl chloride, substantially acid-free, benzoyl peroxide, and ethylene oxide is similarly polymerized at 150 DEG  C.; (3) a mixture of vinyl chloride, vinyl acetate, toluene, benzoyl peroxide, and ethylene oxide (added to give a light-coloured product) is passed under pressure through a porcelain-lined tube at 105-110 DEG  C.; (4) a mixture of vinyl chloride, toluene, benzoyl peroxide, hydrogen chloride, and ethylene oxide is polymerized in the apparatus of (2) at 120-125 DEG  C.; (5) a mixture of vinyl chloride, toluene, benzoyl peroxide and hydrogen chloride is polymerized similarly in an enamel-lined tube at 105-110 DEG  C.; (6) a solution containing vinyl chloride, toluene, benzoyl peroxide, and formic acid is passed under pressure through a lead-lined tube at 110-115 DEG  C.; (7) the formic acid in (6) is replaced by benzoic acid; (8) a mixture of vinyl chloride, vinyl acetate, toluene, benzoyl peroxide, hydrogen chloride, and ethylene oxide is polymerized at 115-120 DEG  C. in a lead-lined tube; (9) a mixture of styrene, acetic acid, and ethyl benzene is heated to 110-120 DEG  C. for 72 hours; (10) a mixture of equal quantities of acid-free vinyl chloride and vinyl chloride containing acid equivalent to 1 per cent of hydrochloric acid, together with toluene and benzoyl peroxide is passed under pressure through an enamel-lined tube at 105-110 DEG  C.