Patent GB-640192-A (GB)
Title: Improvements in or relating to the manufacture of peroxidic compounds
IPC: F02B47/00
Filed: 1947-12-11
Abstract: Catalysts for the polymerization of unsaturated organic compounds comprise peroxides of the formula <FORM:0640192/IV (a)/1> where R1 is a tertiary organic radical, R2 is an organic radical, R3 is H or a hydrocarbon radical, and X is OH or -O-O-R4, where R4 is a tertiary organic radical.  The preparation of a number of such compounds is described (see Group IV (b)) including di-tertiary butyl isopropylidene peroxide, di-tertiary butyl sec.-butylidene peroxide, a ,a -dimethyl-a 1-hydroxydiethyl peroxide, 2-hydroxy-2-tertiary butyl peroxy valeric acid, and 2-methyl-2-hydroxy-4,4-di-tertiary butyl peroxy pentane. Polymerizable compounds include the mono-olefinic, e.g. styrene, a -methyl styrene, vinyl and allyl derivatives, nitriles and esters of acrylic and a -substituted acrylic acids, di- or poly-olefinic unconjugated compounds, e.g. unsaturated polyesters of saturated polybasic acids and polyethers of saturated polyhydric alcohols, unsaturated esters of unsaturated acids, and such compounds as vinyl, allyl, and methallyl esters of phosphoric acid and the ortho acids of silicon and boron, and conjugated di- or polyolefinic compounds, e.g. butadiene, chlorbutadiene, isoprene, and homologues.  Copolymers may also be prepared.  The peroxides may be used in amount of 0.01-5 per cent or more, either alone or with known peroxide catalysts.  Plasticizers, stabilizers, lubricants, dyes, pigments, and fillers may be added before or during polymerization, which may be effected in dispersion or solution at from room temperature to above 200 DEG C.ALSO:Peroxides of the formula <FORM:0640192/IV (b)/1> where R1 is a tertiary organic radical, R2 is an organic radical, R3 is H or a hydrocarbon radical and X is OH or -O-O-R4, where R4 is a tertiary organic radical, are prepared by reacting a tertiary organic hydroperoxide with an organic compound containing a carbonyl group in an acid-reacting medium.  Tertiary alkyl hydroperoxides are preferred reactants and include tertiary butyl and amyl hydroperoxides, and hydroperoxides formed by substitution of -O-O-H for H on one or more tertiary C atoms of, for example, 2-ethyl-butane, 2- or 3-methyl-pentane, 2,3-dimethylbutane and 2,4-dimethyl-pentane. Halogen-substituted products formed by controlled oxidation in presence of HBr of, for example, 1 - halo - 2 - methyl (or ethyl) - propane, 1 - halo - 2 - (or 3-) methyl - butane and 2 - halo - 3 - methylbutane, and substitution products containing hydroxyl, carboxyl, aryl, alkaryl, aralkyl or alicyclic radicals are also included.  The preferred carbonyl compounds are saturated aliphatic and alicyclic aldehydes and ketones, including hydroxy aldehydes and ketones, e.g. lactic aldehyde, hydracrylic aldehyde and acetaldol, acetyl, propionyl and butyryl carbinols, acetoin, diacetone alcohol, acetopropyl (or butyl) alcohol, and hydracetal methyl ethyl ketone. Dicarbonyl compounds such as acetyl acetone, aldehyde and ketone acids, e.g. pyruvic, acetoacetic, levulinic and mesitonic acids, and aromatic compounds such as benzaldehyde may also be used. Acid-acting catalysts comprise sulphuric, phosphoric, hydrochloric, hydrobromic and benzene sulphonic acids.  Sulphuric acid of 50-75 per cent concentration is suitable.  Temperatures are, for example, -10 DEG  to 35 DEG  C.  A dehydrating agent such as calcium chloride may favour the reaction.  The products are of use as additives to Diesel fuels and as polymerization catalysts.  In examples, tertiary butyl hydroperoxide is reacted, in the presence of concentrated hydrochloric acid and calcium chloride, with acetone, methyl ethyl ketone, acetaldehyde and levulinic acid yielding respectively di-tertiary butyl isopropylidene peroxide, di-tertiary butyl sec.-butylidene peroxide, a ,a -dimethyl-a 1-hydroxy diethyl peroxide and 2-hydroxy-2-tertiary butyl peroxy valeric acid.  With diacetone alcohol, in the presence of aqueous sulphuric acid, the product is 2-methyl-2-hydroxy-4,4-di-tertiary butyl peroxy pentane.ALSO:Additives to improve the cetane value of Diesel fuels comprise peroxides of the formula <FORM:0640192/III/1> where R1 is a tertiary organic radical, R2 is an organic radical, R3 is H or a hydrocarbon radical, and X is OH or -O-O-R4, where R4 is a tertiary organic radical.  The preparation of a number of such compounds is described (see Group IV (b)) including di-tertiary butyl isopropylidene peroxide, di-tertiary butyl sec.-butylidene peroxide, a ,a -dimethyl-a 1-hydroxydiethyl peroxide, 2-hydroxy-2-tertiary butyl peroxy valeric acid, and 2-methyl-2-hydroxy-4,4-di-tertiary butyl peroxy pentane.