Patent GB-1143404-A (GB)
Title: Polymer dispersion
Inventor: CLARKE MICHAEL RAYMOND
IPC: C08F2/06
Filed: 1965-02-12
Abstract: 1,143,404. Polymer dispersions; polyamides. BALM PAINTS Ltd., and IMPERIAL CHEMICAL INDUSTRIES Ltd. 2 Feb., 1966 [12 Feb., 1965], No. 6289/65. Headings C3P and C3R. Stable dispersions of particles of synthetic polymer in inert organic liquid in which the polymer is insoluble are prepared by forming the particles in the liquid in the presence of a dissolved polymeric stabilizer containing polar groups, the disperse polymer being one containing polar groups provided by a monomer capable of entering into strong specific interaction (as defined) with polar groups in the stabilizer so as to cause the stabilizer to be bonded to the polymer particles and provide around them a stabilizing steric barrier at least 12 Angstroms thick. The particles are preferably formed by polymerizing monomer to produce the insoluble polymer, although they may also be formed by precipitating the preformed polymer in the liquid from solution by addition of a non-solvent, or by evaporating solvent from a solution of the polymer in a mixture of solvent and non-solvent. Examples 1-25 and 28 illustrate the stabilized dispersion polymerization of methyl methacrylate, acrylonitrile, vinylacetate/acrylic acid mixture, and mixtures of methyl methacrylate with dimethylaminoethyl methacrylate, vinylpyridine, methacrylic acid or acrylonitrile in hydrocarbon liquids using azodiisobutyronitrile as polymerization initiator. Example 26 illustrates the stabilized dispersion polymerization in toluene of caprolactam in the presence of sodium. Example 27 illustrates the preparation of a stabilized dispersion of methyl methacrylate - dimethylaminoethyl methacrylate copolymer in hydrocarbon liquid by precipitating the copolymer from solution. The polymeric stabilizers used in the examples are as follows: (a) long chain aliphatic hydrocarbyl acid phosphates (which associate to form a polymeric chain), (b) the product obtained by solution copolymerizing octadecyl methacrylate with methacrylic acid or dimethylaminoethyl methacrylate (c) the product obtained by copolymerizing the condensate of glycidyl methacrylate and carboxyl terminated polylauryl methacrylate (see Specification 1,096,912) with butyl methacrylate and vinylpyridine, and reacting with dimethyl sulphate and sodium hydroxide to introduce quaternary ammonium hydroxide groups, (d) the product obtained by copolymerizing the condensate of 12-hydroxy stearic acid and glycidyl methacrylate with butyl acrylate and vinyl dimethyl phosphate, (e) as for (d) but replacing the vinyl phosphate with vinyl pyridine and quaternizing the product by reaction with methyl bromide, (f) the product obtained by copolymerizing maleic anhydride and styrene, and reacting the anhydride groups with di-(long chain alkyl) amines, (g) the product obtained by half-esterifying the anhydride groups of an octadecene-1/maleic anhydride copolymer with hexadecanol or a mixture of the latter with methoxy polyethylene glycol, or esterifying a related tetradecene-1 copolymer with dodecanol, (h) an octadecene- 1/ maleic anhydride copolymer, (i) the hexadecanolmethoxy polyethylene glycol ester derivative of (g) further reacted with polyethoxylated nonyl phenol, (j) the product obtained by copolymerizing a mixture of stearyl, polyethylene glycol and butyl methacrylates, (k) the sulphobetaine product obtained by reacting a copolymer of ceto-stearyl and dimethylaminoethyl methacrylates with propane sultone, (1) the product obtained by esterifying a lauryl methacrylate/glycidyl methacrylate copolymer with sulphuric acid or phosphoric acid, (m) the product obtained by reacting a maleic anhydride-vinyl methyl ether copolymer with dioctadecylamine or cetyl alcohol, (n) the product obtained by copolymerizing a stearic acidglycidyl methacrylate condensate with methyl methacrylate, (o) the reaction product of a stearyl methacrylate-glycidyl methacrylate copolymer and acetic acid, (p) the product obtained by copolymerizing vinyl toluene and vinyl sulphonic acid, (q) the product obtained by copolymerizing stearyl methacrylate and acrylonitrile, and (r) the polyamide product obtained by reacting pyromellitic anhydride with a di-secondary amine, produced by reducing the nitrile of dimerized drying oil fatty acid in the presence of methylamine, and converting free carboxyl groups of the polymer to salt form by treatment with di-octadecylamine.