| 摘要 |
1,193,488. Polyolefines. POLYMER CORP. Ltd. 24 Oct., 1967 [24 Oct., 1966], No. 48341/67. Heading C3P. In the co-polymerization of ethylene and at least one other monomer in the presence of a catalyst by a continuous process wherein one or more liquid streams are fed into the reaction zone at a rate substantially equal to the product withdrawal rate and the catalyst in the product stream is continuously deactivated, the process is carried out at a constant predetermined temperature between 0‹ C. and 100‹ C. by suitable pre-cooling of at least one feed stream prior to entering the reaction zone, the residence time of the reactants in the reaction zone is from 6 seconds to 6 minutes, and the terminal mixing time (the time from the start of the mixing to the time when the sample achieves uniformity of composition which is not further changed by additional mixing) of the reactants within the reaction zone is not more than one-quarter of the residence time. The catalyst may be a hydrocarbon soluble vanadium compound and an aluminium alkyl halide and the molar ratio of aluminium to vanadium in the catalyst is preferably from 6 :1 to 12 : 1. Preferably an inert solvent such as hexane is used. The reactants may be continuously fed into the reaction zone as two liquid streams, one mixed feed stream comprising solvent, vanadium-containing catalyst and dissolved monomers and the other stream comprising the aluminium-containing catalyst and more solvent. It is preferred that the mixed feed stream is cooled before entering the reaction zone, for instance between 35 and 110‹ C. below the reaction temperature. Suitable monomers are ethylene, propylene or diolefinic monomers such as 1, 4 hexadiene, dicyclopentadiene, norbornadiene, methylene norbornene, ethylidene norbornene, other alkenyl norbornenes, cyclo-octadiene and tetrahydroindene. The copolymer preferably has an ethylene content of from 60 to 76 mole per cent, and 0À5 to 3À0 mole per cent of the third monomer may be present. A suitable reactor is shown in Fig. 1, wherein the feed streams enter the reactor 10 through circumferentially spaced inlet apertures 22. The feed streams are rapidly mixed by the impeller blades 21, and the product stream leaves the reactor via the orifice 16. By insertion of thermometers into the apertures 23 and 24, the reaction temperature may be measured. In the examples, terpolymers of ethylene, propylene and dicyclopentadiene are prepared using a catalyst system comprising vanadium oxychloride and aluminium ethyl sesquichloride or aluminium ethyl dichloride or aluminium diethyl chloride. The product stream leaving the reactor is treated with ethanol to deactivate the catalyst, followed by further additions of an anti-oxidant and acetic acid. The polymer product is obtained by the separation and steam stripping of the organic phase. The product may be compounded and vulcanized in a standard vulcanization recipe, with oil, carbon black, accelerators, activators and sulphur.
|
