Patent GB-1093074-A (GB)
Title: Graft polymers
IPC: C08F255/06
Filed: 1964-11-03
Abstract: In a graft terpolymer which consists of a terpolymer and at least one grafted monomer and which is sulphur-curable to an elastomeric oil- and solvent-resistant vulcanizate, the terpolymer consists of at least 20 weight per cent ethylene, at least 15 weight per cent of a C3-C10 aliphatic alpha olefin, and at least 0.01 moles per 100 g. of said terpolymer and not over 20 weight per cent thereof of a non-conjugated diolefin, and the graft monomer is a polar ethylenically unsaturated free-radical polymerizable compound containing one or more hetero-atoms in the molecule and preferably constituting 0.5-35 weight per cent of the total graft terpolymer. The graft monomer may be a C4-C8 unsaturated ester (e.g. the methyl or ethyl esters of acrylic, methacrylic, and alpha-chloroacrylic acids), a C3-C6 unsaturated nitrile (e.g. acrylonitrile, methacrylonitrile), C2-C5 unsaturated halides (e.g. vinyl chloride, vinylidene chloride), C4-C6 vinyl esters (e.g. acetate), vinyl ethers, vinyl pyridine, C3-C6 allyl compounds (e.g. allyl acetate, allyl alcohol, allyl chloride, methallyl acetate, allyl amine), ethylene maleate, maleic anhydride, acrylamide, methacrylamide, diethylaminoacrylamide, diethylaminoethyl acrylate, sodium vinyl sulphonate, and C5-C8 unsaturated silanes.  The non-conjugated diolefin may have 6-15 carbon atoms and may be dicyclopenta-2-diene, tetrahydroindene, 5 - methylene - 2 - norbornene, 5-vinyl-2-norbornene, 5(31-butene)-norbornene, 2 - methyl - norbornadiene, 2,4-dimethyl - 2,7 - octadiene, 11 - ethyl - 1,11-tridecadiene, 3 - methallyl cyclopentene, 1,4-hexadiene, and 3 - (21 - methyl - 1 - propene) cyclopentene.  A number of alpha olefins are mentioned (propylene 5,6,6-trimethyl-1-heptene &c.).  The graft copolymer is made by reacting said terpolymer at an elevated temperature with a free-oxygen-containing substance in the presence of a non-peroxidic free-radical initiator thereby forming a terpolymer hydroperoxide, lowering the temperature of the reaction mixture to below the decomposition temperature of said initiator, then contacting the mixture with said polar ethylenically unsaturated free-radical polymerizable compound containing one or more hetero-atoms in the molecule.  The free-oxygen containing substance may be oxygen, and the initiator an organic azo compound.  The terpolymer hydroxide may be at least partly decomposed by contacting with a redox substance prior to contacting it with said unsaturated compounds.  A preferred embodiment comprises reacting the said terpolymer at about 60-90 DEG  C. with a free-oxygen-containing gas in the presence of azobisisobutyronitrile, thereby forming hydroperoxide groups along the main chains of the macromolecules in said terpolymer, cooling the resulting mixture to 10-50 DEG  C., contacting the mixture with an iron salt and an organic reducing agent thereby at least partly decomposing the hydroperoxide groups along the main chains of said macromolecules, and contacting the reaction mixture with excess acrylonitrile until the terpolymer contains at least 0.5 weight per cent combined acrylonitrile, and recovering said terpolymer essentially free of polyacrylonitrile.ALSO:A coating for wires and cables and a lining for metal or plastic pipes comprises a vulcanized graft terpolymer. The graft terpolymer consists of a terpolymer and at least one grafted monomer, said terpolymer consisting of at least 20 wt. % ethylene, at least 15 wt.% of a C3-C10 aliphatic alpha olefin, and at least 0.01 gram moles per 100 grams of said terpolymer and not over 20 wt. % thereof of a nonconjugated diolefin, said graft monomer being a polar ethylenically unsaturated free-radical polymerisable compound containing one or more hetero-atoms in the molecule.  The graft monomer may be a C4-C8 unsaturated ester (e.g. the methyl or ethyl esters of acrylic, methacrylic, and alpha-chloroacrylic acids), a C3-C6 unsaturated nitrile (e.g. acrylonitrile, methacrylonitrile), C2-C5 unsaturated halides (e.g. vinyl chloride, vinylidene chloride), C4-C6 vinyl esters (e.g. acetate), vinyl ethers, vinyl pyridine, C3-C6 allyl compounds (e.g. allylacetate, allyl alcohol, allyl chloride, methallyl acetate, allyl amine), ethylene maleate, maleic anhydride, acrylamide, methacrylamide, diethylaminoacrylamide, diethylaminoethyl acrylate, sodium vinyl sulphonate, and C5-C8 unsaturated silanes.  The non-conjugated diolefin may have 6-15 carbon atoms and may be dicyclopentadiene, tetrahydroindene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5(3\sv-butene)-2-norbornene, 2-methyl-norbornadiene, 2,4-dimethyl-2,7-octadiene, 11-ethyl-1, 11-tridecadiene, 3-methallyl cyclopentene, 1,4-hexadiene, and 3(2\sv-methyl-1-propene)cyclopentene.  A number of alpha olefins are specified (propylene, 5,6,6-trimethyl-1-heptene &c.).