Patent GB-934742-A (GB)
Title: Improvements in or relating to hydrocarbon copolymers
IPC: C08F210/00
Filed: 1961-11-22
Abstract: A sulphur-curable copolymer of (a) ethylene, (b) at least one alpha monoolefine of the formula R-CH=CH2 where R is an alkyl radical containing not more than eight carbon atoms and (c) at least one 2-alkylnorbornadiene containing 8 to 24 carbon atoms, said copolymer having an iodine number between 5 and 60 and containing 20 to 72,5% by weight of ethylene units, 25 to 77,5% by weight of a -monoolefine units and not more than 20% by weight of norbornadiene units, is prepared by copolymerizing the said monomers in an inert solvent medium and in the presence of a co-ordination catalyst obtained by mixing vanadium tetrachloride or oxytrichloride with a compound of the formula X3Al or X2Al Y where the X groups are alkyl groups containing 1 to 12 carbon atoms and Y is a chlorine or bromine atom. Preferably the temperature is between 20 DEG  and 100 DEG C. and the pressure is atmospheric or superatmospheric.  Lists of suitable a -monoolefines and 2-alkylnorbornadienes having the structural formula <FORM:0934742/IV(a)/1> where R1 is an alkyl radical containing 1 to 17 carbon atoms, are given.  The norbornadienes are obtained by heating alkyl acetylenes R1=C=C-H (where R1 is as above) with cyclopentadiene in the absence of a polymerization initiator, the temperature preferably being 175 DEG  to 225 DEG C.  The relative proportions of the vanadium salt and the organometallic compound forming the co-ordination catalyst may be varied so that the molar ratio of aluminium to vanadium is between 1:1 and 10:1.  Oxygen, water vapour and carbon dioxide should be excluded from the p reaction zone.  Tetrachloroethylene is the preferred solvent but liquid paraffins, cycloparaffins and fluorochloro-substituted liquid paraffins may also be used.  An ethylene/propylene/2-methylnorbornadiene copolymer may be obtained by passing a mixture of ethylene and propylene gases, previously freed from oxygen, water vapour and other contaminants reactable with aluminium triisobutyl, below the surface of tetrachloroethylene in a glass reaction vessel through which nitrogen has been passed until the tetrachloroethylene is saturated.  2-methylnorbornadiene, aluminium triisobutyl and vanadium oxytrichloride are then added in turn to the tetrachloroethylene solution of ethylene and propylene. The reaction occurs immediately, the concentration of the polymer being 1 to 5% by weight after 20 to 80 minutes.  In general all the norbornadiene may be present before the catalyst is added or all or part of it may be added during the copolymerization, this introduction may be continuous or intermittent.  The catalyst is deactivated by the introduction of a low molecular weight alcohol, e.g. isopropanol or n-butanol, to the reaction mass and the copolymer solution is extracted with dilute HCl, washed with water and the solvent then flashed off.  An antioxidant, e.g. 2,21-methylenebis(6-tert-butyl-4-methylphenol) or 4,41-thiobis(2-tert-butyl-5-methylphenol) is incorporated prior to the drying operation.  The copolymers may alternatively be prepared by a continuous process.  The copolymers may be cured with sulphur or a free radical cure may be employed.  In the latter case a free radical generator, e.g. dicumyl peroxide, is mixed with the copolymer and the mixture heated to 50 DEG  to 175 DEG C. for 30 minutes to several hours.  A free radical acceptor, e.g. an N-substituted maleimide, an N,N1-substituted bismaleimide, an N,N1-substituted bisacrylamide, a cyclic triacryloylhexatriazine or mixtures thereof may be added. Compounding agents and other curing agents may be incorporated with these copolymers at the time they are cured, e.g. carbon black, titanium dioxide, silica, zinc oxide, stearic acid, tellurium diethyl dithiocarbamate, tetramethyl thiuram disulphide and N-phenyl-beta naphthylamine.