Patent GB-914252-A (GB)
Title: Copolymers of mono unsaturated polyesters and unsaturated monomers
IPC: C08F214/00
Filed: 1958-12-23
Abstract: The invention comprises a graft copolymer of (1) 2-60% by weight of a mono-unsaturated polymer comprising a polyester chain made up of an average of more than two consecutively repeating units per molecule, derived by the self-condensation of an epsilon-caprolactone in which any substituents on the caprolactone chain carbon atoms are only hydrocarbon groups, and having on one end of the chain an unsaturated CH2=C < group containing up to 5 carbon atoms with (2) 98-40% by weight of at least one monomeric compound containine a CH2=C < group. The unsaturated lactong polyester may have a molecular weight of 200-10,000 (preferably 500-3,500) and is represented by the formula <FORM:0914252/IV(a)/1> <FORM:0914252/IV(a)/2> wherein X is <FORM:0914252/IV(a)/3> or R11S-; Y is -H, <FORM:0914252/IV(a)/4> or alkyl; X1 is <FORM:0914252/IV(a)/5> Y1 is <FORM:0914252/IV(a)/6> n is greater than 2; R is -H or alkyl (preferably containing a maximum of 10 carbon atoms); R1 is -H or an alkyl group of less than 3 carbon atoms; R11 is an alkyl group; and wherein either X or Y, but not both, contains a CH2=C < group.  The lactone polyesters are made by polymerizing an epsilon-caprolactone in the presence of an initiator containing a single active hydrogen atom, e.g. water or aqueous mineral acids, a monohydric alcohol, a di-substituted amine, a monocarboxylic acid (which may be unsaturated), hydrogen sulphide, a mercaptan, a thio acid, or the hydroxides of sodium potassium or ammonium. Terminal hydroxy groups in the lactone polyester may be converted to alkoxy groups by reaction with an alkyl halide.  If the initiator used is other than an unsaturated monocarboxylic acid, an unsaturated group is introduced into the lactone polyester, e.g. (a) by esterifying a hydroxy terminated polyester with acrylic, methacrylic or ethacrylic acid or an acid chloride thereof; (b) by effecting ester interchange between a polyester having a terminal ethyl ester group and vinyl acetate; or (c) by reacting a hydroxy terminated polyester with acetylene to produce a terminal vinyloxy group.  Following acrylation or vinylation, those polyesters having carboxyl groups may have their hydrophilic characters reduced by treatment with an alcohol or amine (possibly after addition polymerization has been effected).  The monomer with which the unsaturated lactone polyester is copolymerized may be vinyl chloride and/or vinylidene chloride, vinyl fluoride or bromide, vinylidene fluoride or bromide, vinyl acetate, vinylidene cyanide, acrylonitrile, methyl or ethyl acrylate, acrylamide, methacrylamide, N:N1-dimethylacrylamide, ethylene, propylene, styrene, vinyl cyclobutane, a fluorethylene, butadiene, isoprene or cyclopentadiene. Copolymerization is preferably effected in the presence of inorganic or organic peroxides, hydroperoxides, persulphates, perborates, alkyl borane/oxidant combinations or silver alkyl/oxidant combinations. Copolymerization may be effected in mass, in solution or in suspended or dispersed forms, possibly in water, aqueous alcohol or aqueous anti-freeze solutions in the presence of a suspending agent (e.g. polyvinyl alcohol, gelatine, bentonite, clay or an organic sulphate or sulphonate compound).  In Examples, (1)-(4) and (6) caprolactone or a methyl-substituted derivative thereof is polymerized by heating it in the presence of dilute sulphuric acid, the resulting polyester esterified with acrylyl chloride and the product copolymerized with vinyl chloride in aqueous medium containing isobutyl naphthalene sodium sulphonate, gelatine, sodium bicarbonate and caprylyl peroxide-the copolymers may be blended with dioctyl phthalate or dibutyl tin laurate; (5) caprolactone is polymerized by heating it in the presence of tetrabutyl titanate (catalyst) and butanol (initiator), the resulting polyester esterified with acrylyl chloride and the product copolymerized with vinyl chloride as in Example 1; (7) an acrylated methyl-substituted caprolactone polyester is copolymerized with vinylidene chloride or acrylonitrile.