Patent GB-604544-A (GB)
Title: Process for polymerizing unsaturated organic compounds
IPC: C08F4/38
Filed: 1945-11-26
Abstract: Unsaturated organic compounds which can be polymerized using an organic peroxide catalyst are polymerized alone or together in the presence of at least two different organic peroxides having their maximum catalytic effectiveness at substantially different temperatures, the polymerization being effected through a temperature range which includes temperatures at which each of the organic peroxides of the said combination in the proportion in which the particular catalyst is used therein, is more effective than the other catalyst or catalysts of the said combination in the proportion or proportions in which it or they are used therein.  Preferably the range includes the temperature at which each of the catalysts of the said combination exerts its maximum effectiveness.  As one catalyst may be chosen an organic peroxide having no tertiary alkyl group attached directly to the peroxy radical, e.g. benzoyl, acetyl, benzoylacetyl and lauroyl peroxides and as another in the combination may be chosen a peroxide having at least one tertiary carbon atom attached directly to the peroxy radical, e.g. t-butyl-, t-amyl-hydroperoxides, analogues and homologues and similar peroxides having halogen, hydroxy aryl, alkoxy, alkaryl, aralkyl and/or alicyclic radical substituents. Other peroxides specified are di(tert. - butyl)-, di(tert. - amyl)-, di(methyl-2 - pentyl - 2)-, di(methyl - 3 - pentyl - 3)-, di (ethyl - 2 - butyl - 2) - peroxides, di(phenyl - 1 - methyl - 1 - propyl - 1) - and di(phenyl - 1 - methyl - 2 - propyl - 2)-peroxides, a ,a  - di - methyl - a 1 - hydroxy di-ethyl- and 2 - methyl-2 - hydroxy, 4,4-di-tert.-butyl peroxy pentane, and tert.-butyl acetyl-, and tert.-butyl benzoylperoxides, di(tert.-butyl)-sec.-butylidene peroxide, 2,2 - di(tert. - butyl - peroxy) - propane, and halogen derivative of such compounds. Monomers which may be so polymerized are methyl acrylate, methyl methacrylate, styrene, dichlorostyrene, vinyl acetate, butyrate, and other esters, allyl and polyallyl esters and substitution derivatives of these, polyhydric alcohol esters of acrylic, methacrylic and crotonic acids, vinyl, allyl and methallyl esters of these same acids, esters of allyl, methallyl, ethallyl, chlorallyl, buten-, pentenhexen-, propen, hepten, octen, alcohols and substitution derivatives of these, crotyl, tiglyl, cinnamyl, cyclo-penten and cyclo-hexen alcohols and derivatives thereof, vinyl and vinyl type alcohols, propargyl, pentyn and hexyn alcohols, with polycarboxylic acids such as oxalic, malonic, pimelic, glutaric, suberic, agelaic, tricarballylic acids, phthalic and substitution derivatives thereof, dilactic, dihydracrylic, sulphonyl containing polycarboxylic acids, and many mixed esters, di-isopropenyl phthalate, and methyl, ethyl, propyl, cyclohexyl and benzyl esters of acrylic and like acids, itaconic and citraconic acids, allyl- and vinyl-type esters of ortho-boric, silicic, phosphoric and sulphuric acids, butadiene, isoprene, 2-methyl-1,3-pentadiene, heptadienes and octadienes. Reduced or superatmospheric pressures may be used.  Plasticizers, solvents, dyes, pigments, natural resins, cellulose nitrate, acetate or mixed cellulose esters, ethyl cellulose, polyamides, polyesters, urea - aldehyde, melamine - aldehyde, phenol - aldehyde and alkyd resins may be added.ALSO:Hydroperoxides may be prepared by catalytic oxidation by hydrogen bromide of 2-ethyl butane, 2-methyl-pentane, 3-methyl-pentane, 2,3-dimethyl butane, 2,4-dimethyl pentane, 1-halo-2-methyl butane, 1-halo-3-methyl butane and 2-halo-3-methyl butane, or by heating tert. alkyl alcohol with hydrogen peroxides, or by absorbing isobutylene in sulphuric acid and reacting with hydrogen peroxide.  Ditertiary alkyl peroxides may be prepared by oxidizing 2-methyl butane, isobutane, 2-ethyl butane, and halogen derivatives thereof, isopropyl benzene, 1-phenyl-1-ethyl propane or 1-phenyl-2-methyl propane, viz. oxygen, oxygen yielding compounds in the presence of hydrogen bromide or chloride, or by reacting a tert. alkyl hydroperoxide with a substituted or unsubstituted tert. alcohol in the presence of an acid substance, such alcohols being tert. amyl and butyl alcohols and 2-methyl-pentanol-2, 3-methyl-pentanol-3, 2,3-dimethyl-butanol-2 2,3,3-trimethyl-butanol-2, 1-bromo-2-methylpropanol-2, 1-chloro-2-methyl-propanol-2, 1,1-dichloro-2-methyl-propanol-2, 1,3-dichloro-2-methyl-propanol-2, and other bromo- and chloro-derivatives of similar alcohols, and cyclic alkyl alcohols such as 1-methyl cyclopentanol-1 and 1-methyl cycloheptanal-1,2,2-di-(tert. butyl peroxy) propane is obtained by the action of tert. butyl hydroperoxide on acetone at 0 DEG  C. with hydrochloric acid.  Replacing acetone with methyl ethyl ketone gives di-(tert. butyl butylidene peroxide.  Such peroxides as tert. butyl acetyl and tert. butyl benzoyl peroxides are prepared by reacting the acid chloride with the alkali salt of a tert. alkyl hydroperoxide.