Patent GB-818097-A (GB)
Title: Method for expanding into a foam structure thermoplastic resins and articles thereby obtained
IPC: C08J9/236
Filed: 1956-12-05
Abstract: Granular thermoplastic resins containing a blowing agent incorporated in their discrete particles may be expanded into a foam structure by being mixed with an exothermically selfreacting agent which is inert to the thermoplastic resin; the agent then reacts and generates sufficient heat to soften the thermoplastic resin and to expand the blowing agent.  The thermoplastic resins may be polymers and copolymers of Ar-CR=CH2, where Ar is an aromatic radical and R is hydrogen or methyl; specified thermoplastic resins include polystyrene, polyvinyl toluene, either of which may be cross-linked with divinyl benzene, polymono-and di-chlorostyrene, polydimethyl styrene, polymethyl methacrylate and a copolymer of methyl methacrylate and vinylidene chloride.  Blowing agents specified are CO2, C(Cl2)F2, pentane and other low-boiling hydrocarbons; the CO2 may be incorporated in the resin particles at pressures of 2000 p.s.i. and the others may be incorporated at temperatures of 80-125 DEG  C. or during the polymerization process. The exothermically self-reacting agent, which may contain its own blowing agent as well (e.g. p,p1 - oxy - bis - (benzene sulphonyl hydrazide)) may be any substance or mixture of substances which liberates substantial quantities of heat on physical or chemical intra- or self-reaction; particularly suitable are epoxy resins, i.e. the reaction products of polyhydric phenols or alcohols with epihalohydrins, polyhalohydrins or polyepoxides (e.g. bisphenol A- or resorcinol-epichlorhydrin, epoxylated glycerol, or epoxylated novolaks), such partial polymers being mixed with curing agents such as substituted formaldehydes, polyhydric phenols, polybasic acids, polyamines and polyamides (e.g. diethylene triamine, triethylene tetramine, mixtures of the two, and dipropylene triamine); a phenol-aldehyde precondensate with an aqueous phenolsulphonic acid activator may also be used.  Other components which may be present are coolants to avoid local over-heating (e.g. ethanol, methanol) and wetting-agents.  The process may be carried out in a wide variety of moulds, e.g. a hollow brass mould, an open top fibre board drum, against glass fabric in a mould, against metal or thermoplastic resin mould forms, around a pipe in the annular space between the pipe and a larger cylindrical cardboard tube, in an irregularly contoured polystyrene mould form which is itself in a similarly-shaped conventional magnesium oxychloride cement mould but is separated therefrom by a thin film of a copolymer of vinyl and vinylidene chlorides to prevent sticking. In this way composite sandwich structures may be formed; and in general the process provides a porous article with a non-porous outer skin, as the outer surface of the mass is cooled on coming into contact with the mould with the result that at the outer surface the blowing agent is not expanded.  Uses.-Low temperature insulation, e.g. pipes and refrigerators. Marine, e.g. boats, buoys, pontoons, docks and bulkhead fillers. Laminates, e.g. with metal, wood, glass, glass cloth, concrete, and plastics.  Air, e.g. airplane wingtips. Skis.  Protective clothing, e.g. sun hats and safety headgear. Machine cases. Luggage Furniture.  Mannikins.  Advertizing displays. Theatrical props.  Packaging.  Encapsulating electrical components. Oil well casings.  Culvert moulds.ALSO:Granular thermoplastic resins containing a blowing agent incorporated in their discrete particles may be expanded into a foam structure by being mixed with an exothermically self-reacting agent which is inert to the thermoplastic resin; the agent then reacts and generates sufficient heat to soften the thermoplastic resin and to expand the blowing agent.  The thermoplastic resins may be polymers and co-polymers of Ar-CR=CH2, where Ar is an aromatic radical and R is hydrogen or methyl; specified thermoplastic resins include polystyrene, polyvinyl toluene, either of which may be cross-linked with divinyl benzene, polymono- and di-chlorostryene, polydimethyl styrene, polymethyl methacrylate and a copolymer of methyl methacrylate and vinylidene chloride.  Blowing agents specified are CO2, C(Cl2)F2 pentane and other low-boiling hydrocarbons; the CO2 may be incorporated in the resin particles at pressures of 2,000 p.s.i. and the others may be incorporated at temperatures of 80-125 DEG C. or during the polymerization process. The exothermically self-reacting agent, which may contain its own blowing agent as well (e.g. p. p'-oxy-bis-(benzene sulphonyl hydrazide) may be any substance or mixture of substances which liberates substantial quantities of heat on physical or chemical intra- or self-reaction; particularly suitable are epoxy resins, i.e. the reaction products of polyhydric phenols or alcohols with epihalohydrins, polyhalohydrins or polyepoxides (e.g. bisphenol A- or resorcinol-epichlorhydrin, epoxylated glycerol, or epoxylated novolaks), such partial polymers being mixed with curing agents such as substituted formaldehydes, polyhydric phenols, polybasic acids, polyamines and polyamides (e.g. diethylene triamine, triethylene tetramine, mixtures of the two, and dipropylene triamine); a phenol-aldehyde precondensate with an aqueous phenolsulphonic acid activator may also be used.  Other components which may be present are coolants to avoid local over-heating (e.g. ethanol, methanol) and wetting agents.  The process may be carried out in a wide variety of moulds, e.g. a hollow brass mould, an open top fibre board drum against glass fabric in a mould, against metal or thermoplastic resin mould forms, around a pipe in the annular space between the pipe and a larger cylindrical cardboard tube, in an irregularly contoured polystyrene mould form which is itself in a similarly shaped conventional magnesium oxychloride cement mould but is separated therefrom by a thin film of co-polymer of vinyl and vinylidene chlorides to prevent sticking.  In this way composite sandwich structures may be formed; and in general the process provides a porous article with a non-porous outer skin, as the outer surface of the mass is cooled on coming into contact with the mould with the result that at the outer surface the blowing agent is not expanded.  Uses.  Low temperature insulation, e.g. pipes and refrigerators. Marine, e.g. boats, buoys, pontoons, docks and bulkheads fillers. Laminates, e.g. with metal, wood, glass, glass cloth, concrete, and plastics.  Air, e.g. airplane wingtips.  Skis. Protective clothing, e.g. sun hats and safety headgear.  Machine cases. Luggage.  Furniture.  Mannikins.  Advertising displays. Theatrical props.  Packaging.  Encapsulating electrical components. Oil well casings.  Culvert moulds.