Patent GB-691364-A (GB)
Title: Polysaccharide derivatives of substituted dicarboxylic acids
IPC: C08B37/00
Filed: 1950-02-01
Abstract: Monoesters or salts of monoesters of substituted succinic or glutaric acid in the form of a water-dispersible material characterized by each substituent radicle having both a hydrophilic and a hydrophobic group are made by reacting in an alkaline medium a water-dispersible polysaccharide with an anhydride of succinic or glutaric acid containing as the substituent hydrophobic group an alkyl, alkenyl, alkoxy, aralkoxy, aralkyl or aralkenyl group of 5-18 C atoms, or an acyloxy group of 6-19 C atoms, or with the corresponding mono-acid chloride, the remaining carboxy group present after the reaction being the hydrophilic group.  The free acid ester is obtained on treating the salt with acids.  The term polysaccharide includes cellulose, e.g. wood pulp, cotton linters, regenerated cellulose, and hemi-cellulose.  Specified anhydrides are a -benzyl-, a -styryl-, otyloxy-, capryloxy- and a -phenyl acetoxy-succinic anhydrides, the adduct of maleic anhydride with methyl pentadiene and cyclohexane 1,2-dicarboxylic acid anhydride.  Alkalis include inorganic and organic bases, many being specified.  Reaction may be effected by treating the polysaccharide in aqueous alkaline suspension at a preferred pH of 7-11 and at room temperature with quantities of anhydride of 0.1- about 100 per cent of the dry saccharide or by heating the commercially dry saccharide with an alkaline material, e.g. sodium carbonate or trisodium phosphate, and the anhydride, by heating the dried alkali treated saccharide with the anhydride, or treating the starch in an organic liquid such as benzol, with pyridine and the anhydride. The products may be used in aqueous emulsions and as thickeners. In examples, methyl cellulose is treated in aqueous sodium carbonate dispersion with (3) nonenyl, and (12) octenyl succinic anhydride.  The products may be treated with such anhydrides as maleic anhydride, c.f. Specification 631,242, [Group IV(b)], followed by treatment with a reagent such as a bisulphite to introduce a sulphonic acid group, c.f. Specification 688,291, [Group IV (b)].ALSO:Mono-esters or salts of mono-esters of substituted succinic or glutaric acid in the form of water dispersible material characterized by each substituent radicle having both a hydrophilic and a hydrophobic group are made by reacting in alkaline medium a water dispersible polysaccharide with an anhydride of succinic or glutaric acid containing as the substituent hydrophobic group an alkyl, alkenyl, alkoxy, aralkoxy, aralkyl or aralkenyl group of 5-18 C atoms, or an acyloxy group of 6-19 C atoms, or with the corresponding mono-acid chloride the remaining carboxyl group present after the reaction being the hydrophilic group.  The free acid ester may be obtained on treatment of the salt with acids.  The term "polysaccharide" includes gelatinized and ungelatinized starches such as corn, tapioca, potato, wheat, sago, rice and waxy maize, modified or thin-boiling starches and starch derivatives, and dextrins. Specified anhydrides are alpha benzyl-, alpha styryl-, octyloxy-, capryloxy- and alpha phenyl acetoxy-succinic anhydrides, the adduct of maleic anhydride with methyl pentadiene and cyclohexane 1,2-dicarboxylic acid anhydride.  Alkalis include inorganic and organic bases, many being specified.  Reaction may be effected by treating the starch in aqueous alkaline suspension at a preferred pH of 7-11 and at room temperature with quantities of anhydride of 0.1-about 100 per cent of the dry starch, or by heating a commercially dry starch with an alkaline material, e.g. sodium carbonate or trisodium phosphate and the anhydride, by heating a dried alkali-treated starch with the anhydride, or treating the starch in an organic liquid such as benzol with pyridine and the anhydride.  Pregelatinized starch may be dispersed in pyridine and treated with the anhydride.  The products are emulsifiers and thickeners.  In examples: (1) tapioca starch is treated in aqueous sodium carbonate with decenyl succinic acid anhydride; (2) 60 fluidity corn starch in aqueous sodium carbonate is treated with octenyl succinic acid anhydride; (4) 85 fluidity waxy maize in aqueous sodium carbonate is treated with triisobutenyl succinic acid anhydride; (5) a heavy-cooking tapioca British gum is treated in caustic soda with octadecenyl succinic acid anhydride; (6) potato starch is treated in aqueous sodium hydroxide with octenyl succinic acid chloride; (7) an acid converted thin-boiling waxy maize starch is treated in aqueous sodium hydroxide with octenyl succinic acid anhydride; (8) thin-boiling corn starch is treated in aqueous sodium carbonate with the adduct of maleic anhydride p  with methyl pentadiene; (9) corn starch in caustic soda is treated with capryloxy succinic acid anhydride; (10) octenyl succinic acid anhydride in toluene is sprayed into corn starch blended with sodium carbonate, or dried after caustic soda treatment, and the mixture kept at 90-100 DEG  F. for 3 days; (11) gelatinized starch is dispersed in pyridine and treated with noneyl succinic acid anhydride at 100-120 DEG  C.; and corn starch in aqueous sodium carbonate is treated with (13) heptyl glutaric acid anhydride, and (14) benzyloxy succinic acid anhydride.  The products may be treated with such anhydrides as maleic acid anhydride (cf. Specification 631,242), followed by treatment with a reagent such as a bisulphite to introduce a sulphuric acid group (cf. Specification 688,291).ALSO:Monoesters or salts of mono esters of substituted succinic or glutaric acid in the form of a water dispersible material characterized by each substituent radicle having both a hydrophilic and a hydropholic group are made by reacting in an alkaline medium a water dispersible polysaccharide with an anyhyride of succinic or glutaric acid containing as the substituent hydrophilic group an alkyl, alkenyl, alkoxy, aralkoxy, arkayl or aralkenyl group of 5-18 C atoms, or an acyloxy group of 6-19 C atoms, or with the corresponding mono acid chloride, the remaining carboxy group present after the reaction being the hydrophilic group.  The products are used as emulsifying agents, e.g. in emulsion paints.  The free acid ester is obtained on treating the salt with acids.  The term polysaccharide includes gelatinized and ungelatinized starches, e.g. corn, tapioca, potato, wheat, sago, rice and waxy maize, modified or thin-boiling starches, starch derivatives, dextrines, cellulose, e.g. wood pulp, cotton linters and regenerated cellulose and hemi-cellulose.  Specified anhydrides are   -benyl,   -styryl, octyloxy-, capryloxy-and -phenyl acetoxy-succinic anhydrides, the adduct of maleic anhydride with methyl pentadiene and cyclohexane 1, 2-dicarboxylic acid anhydride.  (For the preparation of the esters see Groups IV(a) and IV(b)).  In example 1 the product obtained by treating tapioca starch in aqueous sodium carbonate solution with decenyl succinic acid anyhdride is used to emulsify water and turpentine.  The products may be treated with such anhydrides as maleic anhydride.  Specification 631,242, [Group IV(b)], followed by treatment with a reagent such as a bisulphite to introduce a sulphonic acid group c.f. Specification 688,291, [Group IV(b)].