Patent GB-856580-A (GB)
Title: Improvements in quaternizing polymers
IPC: C08F8/00
Filed: 1957-06-18
Abstract: A heterocylic nitrogen-base polymer composition comprises a quaternizable polymer of a heterocyclic nitrogen-base monomer having the formula:  <FORM:0856580/IV(a)/1> or <FORM:0856580/IV(a)/2> or <FORM:0856580/IV(a)/3> where R is a hydrogen atom or a methyl radical, and each R1 is a hydrogen atom or an alkyl radical, the combined R1 groups having not more than 12 carbon atoms, or a quaternizable copolymer comprising a mixture of a copolymerizable monomer having the formula I, II or III and a material copolymerizable therewith together with, if desired, up to 50% by weight of the total monomeric material, of other copolymerizable material, and a quaternizing agent comprising a partially halogenated hydrocarbon which quaternizes said heterocyclic nitrogen-base polymers or copolymers with a mould-corroding effect and, as an inhibitor of such mould corrosion, a metal N-substituted dithiocarbonate having the formula:  <FORM:0856580/IV(a)/4> wherein R is a hydrogen atom or an alkyl, aryl, cycloalkyl, aralkyl, alkaryl or alkylcycloalkyl radical or both R's together with the nitrogen atom form a heterocyclic ring, the R groups having a total of 1 to 20 carbon atoms, Me is a metal and n is the valency of the metal.  The polmers can be prepared in aqueous emulsion in the presence of soap, potassium persulphate and an aliphatic mercaptan, after which a short-stopping agent and an antioxidant are added.  Heterocyclic monomers specified are 2-vinyl pyridine, 2-methyl-5-vinylpyridine, 3-ethyl-5-vinyl-pyridine, 5-ethyl-2-vinylpyridine, 4-methyl-3-vinyl-pyridine, 2, 3, 4-trimethyl-5-vinyl-pyridine, 2-isopropenylpyridine, 5-propyl-2-isopropenyl-pyridine, 2-octyl-5-vinyl pyridine, 5-dodecyl-2-vinyl-pyridine, 2-vinylquinoline, 8-ethyl-2-vinylquinoline, 4-hexyl-5-vinylquinoline, 1-vinyl-isoquinoline and 5-methyl-1isopropenyl-isoquinoline, Suitable copolymerizable materials are conjugated dienes; a methyl styrene; halogen-, alkyl- and alkoxysubstituted styrenes; acrylonitrile; methyacrylonitrile; methyl acrylate or methacrylate; ethyl acrylate or methacrylate; methyl vinyl ketone; methyl ispropenyl. ketone and methyl vinyl ether.  The conjugated dienes include 1, 3- butadiene, isoprene, piperylene, methylpentadiene, 2, 3-dimethyl - 1, 3-butadiene, chloroprene. conjugated diolefines having, for example, 8 carbon atoms, and alkoxy and cyano derivatives of olefines. Specified quaternizing agents are 1, 2-dibromocyclohexane; 1-methyl 2,3-dichlorocyclopentane, methyl iodide, methyl bromide, ethyl iodide, propyl iodide, hexyl iodide, nonyl iodide, cetyl bromide, benzyl chloride, benzal chloride, benzotrichloride, halogenated xylenes, bromoform iodoform, chloroform; 2, 3-dibromopropene-1, 1, 2, 3, 4-tetrabromobutane, hexachlorocyclopentadiene; acetyl chloride, chloracetyl chloride, ethylene chlorhydrin, picryl chloride, benzoyl chloride, benzene sulphonyl chloride, methyl, ethyl and methylbenzene sulphates.  As metals in the N-substituted dithiocarbamate derivatives there are specified nickel, copper, iron, lead, cobalt, zinc, selenium, cadmium, tin, manganese and bismuth.  In a typical example (1) butadiene and 2-methyl-5-vinyl pyridine are copolymerized in an aqueous medium containing potassium fatty acid soap, KOH, KCl, sodium salt of naphthalene sulphonic acid condensed with formaldehyde, ferrous sulphate, ethylenediamine tetraacetic acid, p-menthane hydroperoxide and tert-dodecyl mercaptan.  Portions of the copolymer is milled with carbon black, diphenylamine/acetone reaction product, zinc oxide, stearic acid, sulphur, benzothiazyl disulphide, tetramethyl thiuram disulphide, hexachloro-pxylene, glycol ester of vegetable oil fatty acid (plasticizer) and various amounts nickel dibutyldithiocarbamate.  The mixtures are cured by heating in contact with stainless steel, to observe the amount of pitting produced.