Patent GB-980579-A (GB)
Title: Process for producing thickened acidic, alkaline, or saline aqueous compositions
Inventor: GATZA EUGENE MARION
IPC: E21B43/22
Filed: 1962-09-26
Abstract: Acidic, alkaline or saline aqueous compositions are thickened by the addition of a waterdispersible linear polymer sulphonate, of molecular weight preferably greater than 1000, together with an organic thickening promoter for the polymer sulphonate.  The maximum limits by weight of solute in aqueous compositions which may be thickened according to the invention are respectively 25%, 50%, 35%, 50% for strongly acid, weakly acid, alkaline and saline solutes.  The compositions may be prepared by any of the following alternative means without preference: (a) mixing the polymer sulphonate and thickening promoter into an aqueous solution of an acidio, alkaline or saline electrolyte; (b) mixing both the polymer sulphonate and electrolyte into an aqueous solution of the thickening promoter; (c) mixing together aqueous solutions of the polymer sulphonate, thickening promotes and electrolyte suitable thickening promotes are alkanols, glycols, polyglycols, glycol or polyglycol monoethers, or phenols; cyclic ethers; N,N-dialkyl substituted amides, halogen derivatives of any of the foregoing; anionic surface active agents; an alkanolamine, in the case of alkaline or saline compositions; glycerol or pentaerythritol in the case of acid compositions. Suitable polymer sulphonates may be obtained by (a) polymerizing sulphonated monomers where at least 50% e.g. 60% of the monomer is sulphonated or (b) sulphonating linear or toluene soluble polymers where at least 50% of the units are sulphonatable or (c) sulphonating polymers containing up to 2% of a polyfunctional cross-linking agent in which at least 50% of the units are sulphonatable. Methods (a) and (b) may be used for ethylenically unsaturated compounds or for phenol-formaldehyde condensation products. Particularly exemplified for (b) are polystyrene and certain poly alkyl- and aryl-styrenes, poly vinylnaphthalenes, polychlorostyrenes, copolymers of at least two monoalkenylaromatic compounds with or without a minor proportion of monoethylenically unsaturated non-sulphonatable compounds e.g. isobutylene acrylonitrile, acrylamide, alkyl acrylate and methacrylate.  Compositions which may be thickened according to the invention include the inorganic acids hydrofluoric, hydrochloric, hydrobromic, hydriodic, perchloric, iodic, sulphur-ic, -ous, phosphoric, pyrophosphoric, nitric and arsenic, certain specified organic acids, the alkaline electrolytes ammonium hydroxide, and alkali metal hydroxides, carbonates, phosphates, borates, silicates, and certain saline compositions particularly ferrous chloride, cupric, magnesium, sodium, calcium, nickel and zinc chlorides, lead nitrate and copper sulphate.  In an example of the process according to the invention, to an aqueous 20% solution of H2SO4 was added 2% by weight of the ammonium salt of a sulphonated polyvinyltoluene (SPVT) containing 45% active polymer solid having a molecular weight greater than 3 million and an average sulphonate substitution of 98%.  The polymer sulphonate, which had agglomerated on the surface, was dispersed by the addition of 3% by weight of diethylene glycol monoethyl ether.  A homogeneous thickened composition was obtained whose Brookfield viscosity at 25 DEG  C. was 30 centipoises. Other examples relate to thickening of nitric, hydrochloric, phosphorous and phosphoric acids, sodium hydroxide and certain metal chlorides, lead nitrate, copper sulphate and sodium metasilicate.ALSO:Thickened aqueous compositions, suitable for use as oven cleaners, and paint or rust stripping agents consist of (i) dissolved acidic alkaline or saline solutes, (ii) a water-soluble high molecular weight linear polymer sulphonate as thickening agent, (iii) an organic solubilizer for (ii).  Other constituents may be present.  Inorganic and organic acids, inorganic alkaline compounds and inorganic salts are listed for (i), i.e. hydrohalic acids, perchloric, iodic, sulphur-ic,-ons, phosphoric pyrophosphoric, nitric and arsenic acids; acetic, halo-acetic, benzoic, halo and nitro benzoic, acrylic, adipic, bromopropionic, oxalic, maleic, succinic and salicylic acids; ammonium hydroxide, alkali metal hydroxides, carbonates, phosphates, borates and silicates; salts of mono or di-valent elements of Group Ia, IIa, periods 2 to 6, Group Ib, IIb, periods 4 and 5 (Hubbard Periodic Chart of the Atoms, 1954). and in addition Mn, Fe, Co, Ni, Sn, Pb, with anions of strong inorganic acids.  A definition of (ii) is given and examples include the sulphonated products of styrene, alkyl and arylalkylstyrenes and arylchlorostyrenes, vinyl-naphthalenes; of copolymers of styrene with arylvinyltoluene or a -methylstyrene and copolymers of a major proportion (e.g. 60%) of one or more of such monoalkenylaromatic compounds and a minor proportion of non-sulphonotable monoethylenic unsaturated polymerizable compounds-examples of such copolymerizable compounds are isobutylene acrylonitrile, acrylamide and alkyl esters of acrylic and methacrylic acids.  In addition, lightly cross-linked polymers containing e.g. 2% di-vinylbenzene (sulphonic acid) or methylene-bisacrylamide as linking agent may be employed as base polymer for the sulphonation reaction.  The solubilizer (iii) is an alkanol, glycol, polyglycol, ether of same, cyclic ether or phenol, N-N-dialkyl substituted amide, halogen derivative of the above, an alkanolamine, glycerol, pentaerythritol or an anionic surfactant containing alkyl or arylalkyl radicals of C7-20 in combination with sulphonate, sulphate, phosphate or carboxylate moieties. Examples 1 and 2 disclose as (1):  H2SO4, HNO3, H3PO3, H3PO4, (COOH)2, CH3COOH; as (ii):  an SPVT (sulphonated polyvinyl toluene); as (iii) diethylene glycol monoethyl ether, or 2-propanol. Examples 5, 6 and 8 describe paint and rust stripping compositions, viz. (5) (i) NaOH, (ii) polymer sulphonate, (iii) diethylene glycol monoethylether and triethanolamine and water; (6) (i) NaOH, (ii) an SPVT, (iii) as in (5), plus methylene chloride and water; (8) (i) NaOH, (ii) an ammonium salt of SPVT, (iii) tetrasodium N-(1,2-dicarboxyethyl) - N - octadecylsulphosuccinamate plus water.  Example 7 discloses an oven-cleaning formulation consisting of sodium metasilicate triethanolamine, diethylene glycol monoethyl ether, methylene chloride, a paraffin wax, an ammonium SPVT and water.ALSO:Thickened aqueous compositions suitable for cleaning metals consist of: (i) dissolved acidic, alkaline or saline solutes, (ii) a water-soluble high molecular weight linear polymer sulphonate as thickening agent, (iii) an organic solubilizer for (ii).  Other constituents may be present.  Inorganic and organic acids, inorganic alkaline compounds and inorganic salts are listed for (i).  A definition and examples of (ii) are given.  The solubilizer (iii) is an alkanol, glycol, polyglycol, ether of same, cyclic ether or phenol, N-N dialkyl substituted amide, halogen derivative of the above, an alkanolamine, glycerol, pentaerythritol, or an amonic surfactant containing alkyl or arylalkyl radicals of C7-C20 in combination with sulphonate, sulphate, phosphate or carboxylate moieties. Examples 1 and 2 disclose (i) H2SO4, HNO3, H3PO3, H3PO4, (COOH)2, CH3COOH (ii) an sulphonated polyvinyl toluene; (iii) 2-propanol, or diethylene glycol monoethyl ether.  Examples 5, 6 and 8 describe paint and rust stripping compositions, viz. (5) (i) NaOH (ii) polymer sulphonate, (iii) diethylene glycol monoethyl ether and triethanolamine plus water; (6) (i) NaOH, (ii) a sulphonated polyvinyl toluene, (iii) as in (5) plus methylene chloride and water; (8) (i) NaOH, (ii) an ammonium salt of sulphonated polyvinyl toluene, (iii) tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulphosuccinamate, plus water.