Patent GB-933621-A (GB)
Title: Improvements in the production of expandable granular materials from thermoplastic synthetic substances
Inventor: KNOBLOCH HORST ERICH
IPC: C09B59/00
Filed: 1959-10-14
Abstract: In a process for the production of expandable granular thermoplastic material with a grain size of 0,2-4 mm., water containing a dispersing agent for organic liquids immiscible with water, and a solution of a thermoplastic resin in a low-boiling organic solvent which forms with water two separate phases and which also contains in solution 2-20% (based on the weight of the thermoplastic resin) of a water-insoluble expanding agent for the resin, are admixed while being kept in steady motion, the organic solvent is removed from the mixture while continuing the steady motion, and the resulting thermoplastic granules are separated from the aqueous phase. Specified thermoplastic resins are polymers of styrene, acrylic and methacrylic acid esters, vinyl chloride, vinylidene chloride, vinyl carbazole, the polycarbonate produced from butane-diol-(1,4), 2,2-di-(p-hydroxyphenyl)-propane and phosgene, a styreneacrylonitrile copolymer, and condensation products of linear polyesters or polyamides.  Chlorpolystyrene may also be used: this is made, as described in Example 1, by leading chlorine into a solution of polystyrene in methylene chloride and expelling the resulting hydrogen chloride by a current of nitrogen.  The resulting solution may be used directly as one component of the mixture by adjusting its pH to 8 by addition of dry ammonia, and adding an expanding agent thereto. Specified solvents are methylene chloride, ethylene chloride, carbon tetrachloride, 1,1,2-trichlorethane, benzene, ethyl acetate, diisopropyl ether and tetrahydrofuran.  Specified expanding agents are the volatile liquid type, such as petroleum ether, pentane, cyclopentane, hexane, cyclohexane, heptane, diethyl ether and carbon tetrachloride, and the decomposable type such as azoisobutyronitrile, diazoaminobenzene and benzene sulphonic acid hydrazide.  The solution of thermoplastic resin may also contain fillers, pigments, dyestuffs, softeners, flame-preventing additives and insecticides.  In one example (2), glycol diglycidyl ether is added as a stabilizer to a chlorpolystyrene solution.  Specified dispersing agents are polyvinyl pyrrolidone, a copolymer of vinyl pyrrolidone and methyl acrylate, gelatin, casein, polyvinyl alcohol, polyacrylic acid (or salts thereof), kaolin, talc, precipitated magnesium hydroxide or barium sulphate, and alkali salts of alkyl sulphonic acids, alkyl naphthalene sulphonic acids and long-chain aliphatic carboxylic acids.  The solvent may be removed from the mixture either during or after mixing, e.g. by leading an inert gas such as nitrogen or carbon dioxide therethrough, or by distilling off under reduced pressure.  The granules may be separated from the aqueous phase by filtering or centrifuging, and may be expanded to form a closed-cell body by heating above the softening-point of the resin and above the temperature at which the expanding agent acts.ALSO:In a process for the production of expandable granular thermoplastic material with a grain size of 0,2-4 mm., water containing a dispersing agent for organic liquids immiscible with water, and a solution of a thermoplastic resin in a low-boiling organic solvent which forms with water two separate phases and which also contains in solution 2-20% (based on the weight of the thermoplastic resin) of a water-insoluble expanding agent for the resin, are admixed while being kept in steady motion, the organic solvent is removed from the mixture while continuing the steady motion, and the resulting thermoplastic granules are separated from the aqueous phase.  Specified thermoplastic resins are polymers of styrene, acrylic and methacrylic acid esters, vinyl chloride, vinylidene chloride, vinyl carbazole, the polycarbonate produced from butane-diol-(1, 4), 2, 2-di-(p-hydroxyphenyl)-propane and phosgene, a styrene-acrylonitrile copolymer, and condensation products of linear polyesters or polyamides.  Chlor-polystyrene may also be used: this is made, as described in Example 1, by leading chlorine into a solution of polystyrene in methylene chloride and expelling the resulting hydrogen chloride by a current of nitrogen.  The resulting solution may be used directly as one component of the mixture by adjusting its pH to 8 by addition of dry ammonia, and adding an expanding agent thereto.  Specified solvents are methylene chloride, ethylene chloride, carbon tetrachloride, 1, 1, 2-trichlorethane, benzene, ethyl acetate, di-isopropyl ether and tetrahydrofuran. Specified expanding agents are the volatile liquid type, such as petroleum ether, pentane, cyclopentane, hexane, cyclohexane, heptane, diethyl ether and carbon tetrachloride, and the decomposable type such as azoisobutyronitrile, diazoamino-benzene and benzene sulphonic acid hydrazide.  The solution of thermoplastic resin may also contain fillers, pigments, dyestuffs, softeners, flame-preventing additives and insecticides.  In one example (2), glycol diglycidyl ether is added as a stabilizer to a chlorpolystyrene solution. Specified dispersing agents are polyvinyl pyrrolidone, a copolymer of vinyl pyrrolidone and methyl acrylate, gelatin, casein, polyvinyl alcohol, polyacrylic acid (or salts thereof), kaolin, talc, precipitated magnesium hydroxide or barium sulphate, and alkali salts of alkyl sulphonic acids, alkyl napthalene sulphonic acids and long-chain aliphatic carboxylic acids.  The solvent may be removed from the mixture either during or after mixing, e.g. by leading an inert gas such as nitrogen or carbon dioxide therethrough, or by distilling off under reduced pressure. The granules may be separated from the aqueous phase by filtering or centrifuging, and may be expanded to form a closed-cell body by heating above the softening-point of the resin and above the temperature at which the expanding agent acts.