Patent GB-788381-A (GB)
Title: Compositions containing epoxy compounds for treating synthetic fibres
IPC: C08L63/00
Filed: 1956-04-06
Abstract: Fibrous material, e.g. of regenerated cellulose, acrylonitrile, vinyl- or vinylidene-chloride and cyanide polymers, polyesters, polyamides, polyester-polyamides, cellulose ethers, esters and ether esters, zein-formaldehyde polymers, polyurethanes, polyethylenes, glass or alginate rayon, are treated with an aqueous composition containing rubber, a polyepoxide having an epoxy equivalence greater than one and an epoxy curing agent.  The rubber may be natural or synthetic, e.g. a butadiene polymer obtained by polymerizing butadiene alone or with another ethylenically unsaturated compound, e.g. styrene, 3,4-dichloro-alpha-methyl sytrene, methyl-methacrylate, acrylonitrile or methyl-isopropenyl ketone, chloroprene, or an isobutylene polymer.  The composition may also include an emulsifying agent, vulcanization agent or accelerator, long lists of which are given in the Specification.  The fibres may be under tension when treated and after treatment may be dried and used in the reinforcement of rubber articles, e.g. tyres or conveyer belts.  The epoxy compounds, long lists of which are given, fall into the following groups: (1) epoxidized triglycerides; (2) polyethers obtained by reacting epichlorhydrin and polyalcohols, e.g. glycerine in the presence of acids and treating the product with alkali; (3) polyethers obtained by reacting epichlorhydrin and polyhydric phenols, e.g. bis-phenol, in the presence of alkali; including glycidyl ethers of novolac resin; (4) condensates of alkylene oxides with polyalcohols or polythioethers; (5) polyethers prepared from epichlorhydrin and a polyhydric phenol which has two hydroxyaryl groups separated by an aliphatic chain of at least 6 carbon atoms, the chain being attached to a nuclear carbon atom of an hydroxy aryl group, e.g. phenols with unsaturated side chains such as cardanol; (6) epoxy esters of polybasic acids; (7) polymers of epoxy monomers containing at least one polymerizable ethylenic linkage, e.g. allyl glycidyl ether polymerized alone or with other unsaturated monomers, e.g. styrene.  The preparation is described of polyepoxides obtained by reacting (A) glycerine and epichlorhydrin in the presence of boron trifluoride, (B) an ethylene oxide/glycerine condensate and epichlorhydrin, (C) 1,2,6-hexane triol and epichlorhydrin, (D) 2,2-bis(4-hydroxyphenyl)propane and epichlorhydrin and (E) allyl glycidyl ether in the presence of ditertbutyl peroxide.  In examples: (1) an aqueous solution containing A, a styrene-butadiene latex, a soluble adduct of D and diethylene triamine as a curing agent is applied to a rayon cord is used in tyre building.  (2) An aqueous dispersion containing polyether, polyethylene glycol monostearate, polyvinyl alcohol, diethylene triamine and rubber latex is applied to rayon cords as in (1). (3) An aqueous emulsion containing polyether D, the polyethylene glycol ether of sorbitan monopalmitate, polyvinyl alcohol, diethylene triamine and latex is used to impregnate tyre cords.ALSO:Fibrous material, e.g. regenerated cellulose fibres, acrylonitrile polymers, vinyl and vinylidene chloride and cyanide polymers, polyesters, polyamides, polyesteramides, cellulose ethers, esters and ether esters and zein-formaldehyde polymers, poly-urethanes, poly-ethylenes, fibre glass, alginates rayon used for making tyre treads, transmission belts, floor tiles, hoses, raincoats are treated prior to curing with an aqueous adhesive composition containing rubber, a polyepoxide having an epoxy equivalence greater than one and an epoxy curing agent.  Rubber is defined as natural or synthetic rubber, e.g. butadiene polymers obtained by polymerizing butadiene alone or with other ethylenically unsaturated compounds, e.g. styrene, 3,4-dichloro alpha methyl styrene, methyl methacrylate, acrylonitrile, methyl isopropenyl ketone; chloroprenes, isobutylene polymers.  The composition also preferably includes emulsifying agents, vulcanization agents and accelerators, long lists of which are given in the Specification.  The epoxy compounds, long lists of which are given, fall into the following groups: (1) epoxidized triglycerides, (2) polyethers obtained by reacting epichlorhydrin and poly-alcohols, e.g. glycerine in presence of acids and treating the product with alkali, (3) polyethers obtained by reacting epichlorhydrin and polyhydric phenols, e.g. bis-phenol in presence of alkali also glycidyl ethers of novolac resins, (4) condensates of alkylene oxides with poly-alcohols or poly-thioethers, (5) polyethers prepared from epichlorhydrin and a polyhydric phenol which has two hydroxyaryl groups separated by an aliphatic chain of at least 6 carbon atoms and with the chain attached by carbon to carbon bond to a nuclear carbon atom of the hydroxy aryl groups, e.g. phenols with unsaturated side chains such as cardanol, (6) epoxy esters of polybasic acids, (7) polymers of epoxy monomers containing at least one polymerizable ethylenic linkage, e.g. allylglycidylether polymerized alone or with other unsaturated monomers, e.g. styrene. The preparation is described of polyepoxides obtained by reacting (A) glycerol and epichlorhydrin in presence of boron trifluoride dissolving the condensate in dioxan containing sodium aluminate, refluxing, filtering off the insoluble material and removing low boiling fractions by distillation; a pale yellow liquid having an epoxy equivalency of 2.17 and epoxide value 0.671 was obtained; (B) an ethylene oxide/glycerine condensate and epichlorhydrin; (C) 1,2,6-hexane triol and epichlorhydrin; (D) 2,2 - bis - (4 - hydroxyphenyl) propane and epichlorhydrin; (E) allyl glycidyl ether in presence of ditertbutyl peroxide.  The above epoxides are used in the following examples: (I) an 18 per cent aqueous solution of A was mixed with a styrene-butadiene latex and a soluble adduct of D and diethylene triamine as curing agent. Water was added to make the solution 11 per cent on solids and the solution was used to pad Rayon tyre cord which was dried and moulded in admixture with a natural rubber stock containing carbon black, sulphur tar, antioxidant, vulcanizers and stearic acid; the moulded specimen had tensile strength of 18.3 lbs.; (II) 100 parts polyether H, 10 parts polyethylene glycol monostearate and 100 parts 5 per cent aqueous solution of polyvinyl alcohol were mixed and 15 parts diethylene triamine added in 100 parts water, the emulsion was used in admixture with rubber latex to treat tyre cords as in (I).  (III) an emulsion was prepared from polyether D, the polyethylene glycol ether of sorbitan monopalmitate, polyvinyl alcohol, diethylene triamine and water and mixed with latex was used to impregnate tyre cords.