Patent GB-1042467-A (GB)
Title: Production of ethylene copolymers containing hydroxyl groups
Inventor: NAARMANN HERBERT
IPC: C08F16/00
Filed: 1963-07-16
Abstract: In a process for the production of ethylene copolymers containing hydroxyl groups, ethylene is polymerized using free radical forming catalysts at temperatures between 30 DEG  and 300 DEG  C. and pressures of more than 10 atmospheres in admixture with up to 50% by weight of the monomers of an ethylenically unsaturated alcohol of formula <FORM:1042467/C3/1> where R1 and R2 are hydrocarbon radicals which may together form components of a carbocyclic ring.  Specified alcohols are 3-methylbuten-1-ol-3, 3 - methylpenten - 1 - ol - 3, 3 - methylhexen - 1 - ol - 3, 3 - methylhepten - 1 - ol - 3, 3 - phenylbuten - 1 - ol - 3, 3 - ethylpenten-1-ol-3, 3 - phenylpenten - 1 - ol - 3, diphenylvinyl carbinol, 1 - vinylcyclohexanol - 1, 3 - n - butylbuten - 1 - ol - 3 and 3 - n - butylpenten - 1 - ol-3. Additional comonomers may also be present, many suitable compounds being listed including vinyl esters, vinyl ethers, acrylic and methacrylic esters, amides and N-methylol amides, maleic acid or anhydride, fumaric acid, itaconic acid, vinyl sulphonic acids and their aryl esters. Specified catalysts are benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl perbenzoate, azodiisobutyronitrile, azo bis-cyclohexanecarboxylic nitrile, azo bis-dimethylbutyronitrile, methyl azo bis-isobutyrate, azo bis-isobutyramide, redox systems of potassium or ammonium persulphate and ascorbic acid or sodium hydrosulphite, or benzoyl peroxide and dimethyl aniline, and oxygen.  Polymerization may be effected in bulk, in emulsion or in the presence of organic solvents, e.g. methanol, ethanol, propanol, t-butanol, glycol, acetone, methyl ethyl ketone, diisobutyl ether, tetrahydrofuran, dioxane, cyclohexane, benzene, toluene, xylene, ethylbenzene, isopropylbenzene, formamide and dimethylformamide.  The copolymers may be mixed with polyethylene, polyacrylates, polyamides, copolymers of ethylene and vinyl acetate, natural and synthetic rubbers, cellulose acetate and fillers, e.g. diatomaceous earth, titanium dioxide and carbon black, and used for moulding, coating and improving paper and textiles.  The polymers may be cross-linked with diisocyanates and dicarboxylic acids.  Examples describe the copolymerization of ethylene with (1) and (2) 3-methylbuten-1-ol-3, 3-phenylbuten - 1 - ol - 3, 3 - ethylpenten - 1 - ol - 3, 1-vinylcyclohexanol - 1 and 3 - methylocten - 1 -ol-3; (3) 3 - methylpenten - 1 ol - 3; (4) 3-methylbuten-1-ol-3 and the curing of the product with hexamethylene diisocyanate; (5) 3-methylbuten-1-ol-3 and acrylic acid; (6) 3-phenylbuten-1-ol-3 and vinyl acetate; (7) 3,4-dimethylpenten-1-ol-3 and the cross-linking of the product with tolylene diisocyanate; (8) 3-phenylbuten-1-ol-3, the cross-linking of the product with hexamethylene diisocyanate and the formation of sulphur vulcanizable products by treating with acetic acid; (9) 3-methylbuten-1-ol-3 and vinyl acetate; (10) 3-isobutylbuten-1-ol - 3; (11) 3 - n - butylbuten - 1 - ol - 3 and n-butyl acrylate and the cross-linking of the product with hexamethylene diisocyanate; and (12) 3-cyclohexylbuten-1-ol-3 and vinyl acetate.