Patent GB-1116728-A (GB)
Title: Improvements in or relating to azidoformates, homopolymers and copolymers thereof and coating compositions containing the same
IPC: C08F20/34
Filed: 1965-12-09
Abstract: The invention comprises homo- and copolymers of unsaturated azidoformates having the formula R(O.CO.N3)x where R is an ethylenically unsaturated hydrocarbon group which may contain ester or ether linkages or be substituted by halogen, and x is an integer of 1-5.  Polymerization can be effected by heating and/or using redox catalysts, e.g. cobalt - cyclohexanone peroxide, iron - benzoin - cumene hydroperoxide or p - menthane hydroperoxide-sodium formaldehyde sulphoxylate, or simple free radical initiators, e.g. acetyl peroxide, azobis-isobutyronitrile and benzoyl peroxide, in bulk, solution or emulsion.  Many ethylenically unsaturated co-monomers are specified.  Examples 5 and 6 relate to homo-polymers of the monazidoformates of 2-hydroxyethyl methacrylate and the triallyl ether of pentaerythritol.  Examples 7-10 relate to copolymers in which the non-azido co-monomers are a -methyl styrene/ethylacrylate, butyl methacrylate, methyl methacrylate/ethyl acrylate and isobornyl acrylate/2-ethyl-hexyl acrylate.  In Example 7, t-dodecyl mercaptan is used in the reaction mixture, and the reaction is short-stopped by the addition of di-t-amyl-hydroquinone. Example 11 relates to a copolymer of 2-azidoformates.  The polymers can be used in coating compositions. In examples, some of the above-mentioned polymers are dissolved in xylene, toluene, and/or benzene, and coatings obtained from these solutions can be cured by baking.  In one case, titanium dioxide is also included in in the composition.ALSO:The invention comprises azidoformates of the formula R(O.CO.N3)x where R is a hydrocarbon group, which may contain ester or ether linkages or halogen substituents, containing at least one polymerizable ethylenically unsaturated group and x is an integer of 1-5. Specified values for R include vinylene, vinylidene, substituted vinylene, substituted vinylidene, vinylakyl and vinylaryl groups and the group (R1O)nZ where R1 is a substituted or unsubstituted vinylene or vinylidene group, a vinylakyl or vinylayl group or an acrylyl or methacrylyl group and Z is the residue of a saturated aliphatic alcohol having a minimum functionality of 2, and n is the functionality of Z minus x and is at least 1.  The azidoformates may be prepared by reacting an ethylenically unsaturated compound containing at least 1 hydroxyl group with phosgene and reacting the resulting chloroformate with a molar excess of an alkali metal azide. Numerous hydroxy compounds are specified.  Examples describe the preparation of the monoazidoformates of 2 - hydroxyethyl methacrylate, the triallyl ether of pentaerythritol and oleyl alcohol, and the tris-azoformate of dipentaerythritol tritungate. The unsaturated azoformates can be polymerized and the polymers used in coating compositions (see Divisions B2, B7, C3 and D1].ALSO:Coating compositions comprise one or more azidoformates of the formula R(O.CO.N3)x where R is an ethylenically unsaturated hydrocarbon group which may contain ester or ether linkages or bear halogen substituents and x is an integer of 1-5, or the homo- or copolymers of such unsaturated azidoformates.  The compositions may also contain other polymeric film-forming materials, e.g. polyolefins, polyhalogenated olefins and polyolefin oxides.  The coating compositions are applied to substrates using conventional techniques and the coated substrate heated to 70-350 DEG .  Examples 12-17 describe coating steel plates and polypropylene plaques with compositions containing the azidoformates of 2-hydroxyethyl methacrylate and the triallyl ether of pentaerythritol or polymers thereof.ALSO:Polyester fibres having an improved adhesion for rubber are obtained by the application of a coating containing one or more azidoformates of the formula R(O.CO.N3)x where R is an ethylenically unsaturated hydrocarbon radical which may contain ester or ether linkages or halogen substituents and x is an integer of 1-5, or the homo- or co-polymers of such unsaturated azidoformates.  The preferred fibres are those comprising polyethylene terphthalate. Fibres spun from blends of polyester and another polymer e.g. nylon, or those obtained from mixed filaments of polyester and e.g. nylon, polypropylene or rayon, may also be used.  The coating composition usually takes the form of an organic solution or aqueous dispersion of the azidoformate, or polymer thereof, and is applied by dipping, spraying or brushing the fibre.  The coating is cured by heating to 70-350 DEG C; curing may be effected after the fibre has been incorporated in a rubber stock.  A second coating which is a mixture of a phenolaldehyde resin and a rubber latex comprising an aqueous dispersion of a vinylaryl monomer/diene monomer/vinyl pyridine monomer terpolymer, may be superimposed on the modified polyester fibre using conventional coating techniques and curing at 120-220 DEG C. Examples 18-25 describe the preparation of polyester fibres having a single azidoformate coating.  Examples 26-33 relate to the application of a second, rubber coating to the modified fibres and the incorporation thereof in rubber stock.