Patent GB-972543-A (GB)
Title: Improvements relating to hydrocarbon copolymers
IPC: C08F10/00
Filed: 1962-09-05
Abstract: The following compounds (1) vanadium tris (acetyl-acetonate), (2) 5, 6-dibromo -1- hexene, and (3) 4, 5-dibromohexene-1, are made by the following methods. In the case of (1) VCl3 is dissolved in dilute sulphuric acid, and the solution added to acetylacetone. After the reaction has ceased, the solution is neutralized with aqueous sodium carbonate, and the precipitated crystals of vanadium tris(acetyl-acetonate) washed with water and air-dried. In regard to (2) a solution of bromine in carbon tetrachloride is added dropwise to a stirred solution of biallyl in carbon tetrachloride at -5 DEG to -10 DEG C.  After the termination of the reaction CCl4 is removed by distillation, and the residue fractionally distilled. The cut boiling at 73 DEG C. (6.5 mm.). Hg was identified as 5,6-dibromo-1-hexene. In regard to (3) a solution of Br2 in CCl4 was added dropwise to 1,4-hexadiene dissolve in CCl4 at -10 DEG  to 0 DEG C.  After the termination of the reaction, excess of the diene and CCl4 are removed by distillation and the residue fractionally distilled. The cut boiling at 65-66 DEG C. (6.0 mm. Hg) was identified as 4,5-dibromohexene-1.ALSO:Normally solid copolymers containing at least 2% by weight of a side-chain substituted halogen, and consisting of monomer units of (1) ethylene, (2) at least one halogenated olefin in which the olefin is either a compound of the formula CH2=CH-CH2-R, where R is a monovalent aliphatic hydrocarbon radical substituted by at least one halogen atom, or a halogenated 2-norbornene having one unsubstituted carbon to carbon double bond, and optionally (3) at least one olefinically unsaturated hydrocarbon monomer, other than ethylene are made by (A) copolymerizing a mixture of the monomers in the presence of a catalyst derived from a vanadium or titanium salt and an aluminium alkyl or halide alkyl, or (B) reacting a copolymer of ethylene and a non-conjugated diene with chlorine, bromine, iodine, hydrogen chloride, hydrogen bromide, or hydrogen iodide. Monomer (2) may be 4-chloro-, or 4-bromo-1- butene, 5-chloro, or 5-bromo -1- pentene, 4-chloro -1-pentene, 4-chloro-, 5-chloro-, 5-bromo-, or 5-iodo-, or 6-fluoro-1- hexene, 7-bromo -1- heptene, 9-bromo -1- nonene, 11-chloro -1- hendecene, 11-bromo -1- hendecene, 11-iodo -1- hendecene, 13-bromo -1- tridecene, 15-bromo -1- pentadecene, 6-bromo -5- bromo-methyl -1- heptene, 5, 5, 5-trichloro -1- pentene, 4, 5-dibromo -1-hexene, 5, 6-dibromo -1- hexene, 4, 4, 5, 5-tetrabromo -1- hexene, or 5, 6-bischloromethyl -2-norbornene, or 5-trichloro-methyl -2- norbornene. The Specification contains extensive lists of other monomers suitable as optional component (3). These monomers may be selected from alpha-olefins, non-conjugated hydrocarbon dienes e.g. dicyclopentadiene, aliphatic dienes containing 6-22 carbon atoms, 5-methylene-2-norbornene and substituted compounds thereof, and 5-alkenyl -2- norbornenes and substituted compounds. The Specification also contains an extensive list of copolymers, and the preparations of 17 copolymers are exemplified. The polymerization is effected in a diluent such as n-heptane, methylene chloride, ethyl chloride, 1,2-dichloroethane, or carbon tetrachloride, and the polymeric product recovered by conventional techniques. The preferred catalysts are vanadium tris (acetyl-acetonate) and diisobutyl aluminium chloride in methylene chloride, vanadium oxytrichloride and triisobutyl aluminium in carbon tetrachloride, and a mixture of vanadium tris (acetylacetonate) and vanadium oxytrichloride with triisobutyl aluminium in carbon tetrachloride. The copolymers can be cured by sulphur, percompounds, N-substituted compounds, and metal oxides. The copolymers prior to curing may be compounded with fillers and pigments such as carbon black, titanium dioxide, and silica. Specification 819,279 is referred to.