Patent GB-954361-A (GB)
Title: Improvements in or relating to ditertiary peroxides
Inventor: TIJSSEN STEPHANUS BERNARDUS
IPC: C08K5/14
Filed: 1960-06-08
Abstract: Ditertiary organic peroxides are prepared by reacting a tertiary hydroperoxide with an olefinic compound of either of the general formulae: <FORM:0954361/C2/1> in which A represents an aromatic or an aliphatic hydrocarbon group having up to 6 carbon atoms and R1, R2, R3 and R4 represent unsubstituted or halogen-substituted alkyl cycloalkyl or aryl groups, or R1 and (or) R2 may be hydrogen, the reaction being effected in a substantially anhydrous medium in the presence of an inorganic acid or an organic sulphonic acid. Specified tertiary hydroperoxides are tertiary butyl- and amyl-hydroperoxides, p-menthane hydroperoxide, cumyl hydroperoxide, and 1-chloro-and 1, 1-dichloro-2-methyl-2-hydroperoxy-propane. Specified olefinic compounds are a -methylstyrene, p-chloro-a -methylstyrene, diisopropenylbenzene, diisobutylene, 2, 5-dimethylhexadiene-1, 5 and dipentene. Specified catalysts are perchloric and sulphuric acids, hydrogen chloride and bromide, boron trifluoride, toluene p-sulphonic acid, benzene sulphonic acid and benzene m-disulphonic acid. If the catalyst is insufficiently soluble in the reaction mixture, the latter may include an aliphatic monocarboxylic acid, e.g. acetic acid. The reaction temperature may be 10-80 DEG C., preferably 40-50 DEG C.  Examples are given in which (1) tertiary butyl hydroperoxide and a -methylstyrene yield cumyl-tert.-butyl peroxide; (2) cumyl hydroperoxide and a -methyl-styrene yield dicumyl peroxide; (3) tertiary butyl hydroperoxide and diisobutylene yield 2-(tert.-butyl peroxy)-2, 4, 4-trimethylpentane; (4) tertiary butyl hydroperoxide and 2, 5-dimethylhexadiene-1, 5 yield 2, 5-di(tert.-butylperoxy)-2, 5-dimethyl-hexane; (5) tertiary butyl hydroperoxide and p-diisopropenylbenzene yield 1, 4-bis (tert.-butyl-peroxyisopropyl)-benzene. The products are useful as catalysts in the production of cross-linked polyolefines and in the vulcanization of natural and synthetic rubbers. Specification 658,522 is referred to.ALSO:As catalysts in the production of cross-linked polyolefines and in the vulcanization of natural and synthetic rubbers, use is made of ditertiary organic peroxides prepared by reacting a tertiary hydroperoxide with an olefinic compound of either of the general formulae: <FORM:0954361/C3/1> <FORM:0954361/C3/2> in which A represents an aromatic or an aliphatic hydrocarbon group having up to 6 carbon atoms and R1, R2, R3 and R4 represent unsubstituted or halogen-substituted alkyl, cycloalkyl or aryl groups, or R1 and (or) R2 may be hydrogen, the reaction being effected in a substantially anhydrous medium in the presence of an inorganic acid or an organic sulphonic acid (see Division C2). Specified tertiary hydroperoxides are tertiary butyl- and amylhydroperoxides, p-menthane hydroperoxide, cumyl hydroperoxide, and 1-chloro- and 1,1-dichloro-2-methyl-2-hydro-peroxy-propane. Specified olefinic compounds for use in the preparation of the catalysts are a -methylstyrene, p-chloro -a - methylstyrene, diisopropenylbenzene, diisobutylene, 2,5-di-methylhexadiene-1, 5 and dipentene. An example is given in which an ethylene-propylene copolymer is vulcanized with carbon black, with or without sulphur, in the presence of 1, 4-bis(tert.-butylperoxyisopropyl)-benzene. Specification 658,522 is referred to.