Patent GB-390045-A (GB)
Title: Improvements in or relating to the vulcanization of rubber
IPC: F16D3/28
Filed: 1932-07-27
Abstract: By passing chlorine into quinhydrone, prepared by adding chromic anhydride to hydroquinone in dilute hydrochloric acid, chlorinated derivatives of p-benzoquinone up to the tetrachloro compound are obtained.  Potassium permanganate, sodium or potassium dichromate with or without sulphuric acid may replace the chromic anhydride. With ferric chloride the reaction can be carried as far as the formation of tetrachlorohydroquinone. Bromo-and iodo-derivatives of p-benzoquinone can be similarly prepared.  The process is also applicable to the preparation of the halogenated derivatives of o-benzoquinone and p-toluquinone.ALSO:Rubber is treated with a quinone haloid, if necessary in the presence of an oxidizing agent, to give it properties similar to those conferred by vulcanization with sulphur.  The term "quinone haloid" includes halogenated quinones, quinhydrones, hydroquinones, addition products of quinone and a halogen, or mixtures of these.  Specified examples are monochlorop-benzoquinone, 2.3-dichloro-p-benzoquinone, 2.5-dichloro-p-benzoquinone. 2.6-dichloro-p-benzoquinone, trichloro-p-benzoquinone, tetrachloro-p-benzoquinone, monobromo-p-benzoquinone, 2.5-dibromo-p-benzoquinone, 2.6-dibromo - p - benzoquinone, tribromo - p - benzoquinone, tetrabromo-p-benzoquinone, trichlorop - toluquinone, tetrabromo - o - benzoquinone, tetraiodo-p-benzoquinone, the corresponding hydroquinones, p-benzoquinone dichloride, and p-benzoquinone dibromide.  When halogenated quinone alone is used in the reaction, half of it is reduced to the corresponding hydroquinone, incapable of combining with the rubber, and extractable with acetone.  By the addition of an oxidizing agent, the quinone is continuously regenerated and all is available for the reaction. With hydroquinones, an oxidizing agent is essential.  Suitable oxidizing agents are lead peroxide, manganese dioxide, mercuric oxide, red lead oxide, thorium oxide, nickelic oxide, cobaltic oxide, ferric vanadate, ferric phosphate, ferric sulphate, ferric oxalate, ferric benzoate.  The presence of alkalies and amines destroys the vulcanizing power of these bodies in the absence of oxidizing agents. The quantity to be added is ordinarily 3-5 per cent. but with highly compounded stocks up to 10 per cent may be necessary.  Vulcanization with the higher halogenated products will take place at room temperatures, but the times and temperatures usual in the vulcanization with sulphur are generally employed.  Numerous examples are given showing proportions, conditions, and properties of various mixes: the following is typical: 100 parts of smoked sheet, 5 parts of a chlorinated p-benzoquinone containing 49-05 per cent Cl., 50 parts of carbon black, 5 parts of pine tar, 1 part of palm oil, and 15 parts of lead peroxide, vulcanized in a press at 145 DEG  C. for 30 mins., gave a tensile of 3505 lbs. per sq. in. and an elongation of 440 per cent.  Hydroquinones with oxidizing agents are particularly suitable for the vulcanization of latex, producing a thixotropic gel.  The new agents may be used in conjunction with sulphur.  Tetrachloro-p-benzoquinone may be prepared as follows: 110 gm. of hydroquinone are added to 3300 cc. of hydrochloric acid; 20 gm. of chromic anhydride crystals are added, and chlorine is bubbled through for 2 hours, when heat is applied and chlorination is continued (10 hours) until a fine yellow precipitate rises to the surface.