Patent GB-494327-A (GB)
Title: Improvements in or relating to protein derivatives
Filed: 1937-01-18
Abstract: Protein derivatives are made by reacting protein with a lower aliphatic aldehyde or ketone and a primary or secondary amine containing less than 9 carbon atoms, preferably an aliphatic amine. The amine and aldehyde or ketone may be reacted together before reacting with the protein.  In examples: (1) methylol piperidine made from formaldehyde and piperidine in the presence of potassium carbonate is reacted with zein mixed with methanol and water; (3) to (7), (11) and (12) zein is reacted with diethylamino-methanol, dibutylamino-methanol, cyclohexylethyl-amino-methanol, piperazine and formaldehyde and ethylamino-methanol; (8) glycinin (soya protein) is reacted with diethylamino-methanol; (10) casein is reacted with methylene dimethylamine (CH3)2N-CH2-N(CH3)2 made fro formaldehyde and excess of dimethylamine.  Other proteins that may be used are gelatine, albumen, globin from blood, hordein from barley or rye, legumen, edestin from cotton or hemp seed, peanut protein, globulins, glutelins, pyrolamines, and conjugated proteins such as casein. Difficulty soluble proteins such as keratin are first partly degraded by alkali or alkaline earth hydroxides, sulphides, or hydrosulphides. Preferably the protein is such as to yield on hydrolysis at least 10 per cent of aspartic and glutamic acids, arginine and lysine.  Other amines mentioned are pyrrolidine, hexamethylene imine, morpholine, tetramethylpiperazine, ethylene diamine, diethylene triamine, triethylene tetramine, benzylamine, xylylenediamine, and b -phenylethylamine, and hydroxyamines such as glucamine, ethanolamine and diethanolamine.  Instead of formaldehyde solution there may be used paraformaldehyde, trioxymethylene, or gaseous formaldehyde; or other aldehydes, such as acetaldehyde, propionaldehyde, isobutyraldehyde, acrolein, chloral, and methacrylic aldehyde; or ketones such as acetone or methyl-ethyl ketone.  If the product is not sufficiently soluble in acids, the process may be repeated upon it, using the same or different aldehydeamine reactants.  The products may be used to make shaped objects such as filaments, and films, or may be used for coating-compositions in which they may be the main or a small ingredient; they may be used as dispersing or emulsifying agents for materials such as oils and waxes or for solids such as pigments; and such compositions may contain also mould or mildew inhibitors, wetting agents, antioxidants, plasticizers, insecticides, adhesives, film-forming materials, &c.  The coating-compositions may be used for treating impervious and pervious surfaces, including textiles; such treated textiles may be secured together usually by the application of heat.  An emulsion of a wax, a fixing agent such as aluminium acetate having the product of the invention as emulsifying agent, may be used for sizing and waterproofing fabrics and for affixing acid dyes to paper.ALSO:Protein derivatives are made by reacting protein with a lower aliphatic aldehyde or ketone and a primary or secondary amine containing less than 9 carbon atoms, preferably an aliphatic amine. The amine and aldehyde or ketone may be reacted together before reacting with the protein.  In examples: (1) methylol piperidine made from formaldehyde and piperidine in the presence of potassium carbonate is reacted with zein mixed with methanol and water; (3) to (7), (11) and (12) zein is reacted with diethylaminomethanol, dibutylaminomethanol, cyclohexylethyl-aminoethanol, piperazine and formaldehyde, and ethylaminomethanol; (8) glycinin (soya protein) is reacted with methylol piperidine; (9) gliadin is reacted with diethylaminomethanol; (10) casein is reacted with methylene dimethylamine (CH3)2N-CH2-N(CH2)2 made from formaldehyde and excess of dimethylamines.  Other proteins that may be used are gelatine, albumen, globin from blood, hordein from barley or rye, legumen, edestin from cotton or hemp seed, peanut protein, globulins, glutelins, prolamines and conjugated proteins such as casein. Difficultly soluble proteins such as keratin are first partly degraded by alkali or alkaline earth hydroxides, sulphides, or hydrosulphides.  Preferably the protein is such as to yield on hydrolysis at least 10 per cent of aspartic and glutamic acids, arginine and lysine.  Other amines mentioned are pyrrolidine, hexamethylene imine, morpholine, tetramethyl piperazine, ethylene diamine, diethylene triamine, triethylene tetramine, benzylamine, xylylenediamine, and b -phenylethylamine, and hydroxyamines such as glucamine, ethanolamine and diethanolamine.  Instead of formaldehyde solution there may be used paraformaldehyde, trioxymethylene, or gaseous formaldehyde; or other aldehydes, such as acetaldehyde, propionaldehyde, isobutyraldehyde, acrolein, chloral, and methacrylic aldehyde; or ketones such as acetone or methylethyl ketone.  If the product is not sufficiently soluble in acids, the process may be repeated upon it, using the same or different aldehyde-amine reactants.  The products may be used to make shaped objects such as filaments, and films, or may be used for coatingcompositions in which they may be the main or a small ingredient; they may be used as dispersing or emulsifying agents for materials such as oils and waxes or for solids such as pigments; and such compositions may contain also mould or mildew inhibitors, wetting agents, antioxidants, plasticizers, insecticides, adhesives, film-forming materials, &c. The coating-compositions may be used for treating impervious and pervious surfaces, including textiles; such treated textiles may be secured together usually by the application of heat.  Treated rayon tyre cord adheres more readily to rubber; treated regenerated cellulose sheets show improved adherence of printing-inks and lacquers; and the compositions may be used as waterproof glues for veneers; an emulsion of a wax, a fixing agent such as aluminium acetate having the product of the invention as emulsifying agent may be used for sizing and waterproofing fabrics and for affixing acid dyes to paper.  The products, with or without a fixing agent may be used as a size for paper, especially as a beater-size, for chalkfilled paper; and a composition containing an aqueous dispersion of titanium oxide and/or other solid (which may be a mildew-preventive such as salicylanilide), a wetting agent, a softener, and a product of the invention as dispersion agent may be used for sizing and delustring fabrics.ALSO:Protein derivatives are made by reacting protein with a lower aliphatic aldehyde or ketone and a primary or secondary amine containing less than 9 carbon atoms, preferably an aliphatic amine.  The amine and aldehyde or ketone may be reacted together before reacting with the protein.  In examples: (1) methylol piperidine made from formaldehyde and piperidine in the presence of potassium carbonate is reacted with zein mixed with methanol and water; (3) to (7) (11) and (12) zein is reacted with diethylaminomethanol, dibutylamino-methanol, cyclohexlethyl-amino-ethanol, piperazine and formaldehyde and ethylaminomethanol; (8) glycinin (soya protein is reacted with methylol piperidine; (9) gliadin is reacted with diethylaminomethanol; (10) casein is reacted with methylene dimethylamine (CH3)2 N-CH2-N (CH3)2 made from formaldehyde and excess of dimethylamine.  Other proteins that may be used are gelatine, albumen, globin from blood, hordein from barley or rye, legumen, edestin from cotton or hemp seed, peanut protein, globulins, glutelins, perolamines, and conjugated proteins such as casein. Difficultly soluble proteins such as keratin are first partly degraded by alkali or alkaline earth hydroxides, sulphides, or hydrosulphides.  Preferably the protein is such as to yield on hydrolysis at least 10 per cent of aspartic and glutamic acids, arginine and lysine.  Other amines mentioned are pyrrolidine, hexamethylene, imine, morpholine, tetramethylpiperazine, ethylene diamine, diethylene triamine, triethylene, tetramine, benzylamine, xylylenediamine, and b -phenylethylamine, and hydroxyamines such as glucamine, ethanolamine and diethanolamine. Instead of formaldehyde solution there may be used paraformaldehyde, trioxymethylene, or gaseous formaldehyde; or other aldehydes, such as acetaldehyde propionaldehyde, isobutyraldehyde, acrolein, chloral, and methacrylic aldehyde; or ketones such as acetone or methylethyl ketone.  If the product is not sufficiently soluble in acids, the process may be repeated upon it, using the same or different aldehyde-amine reactants. The products may be used as dispersing or emulsifying agents for materials such as oils and waxes or for solids such as pigments; and such compositions may contain also mould or mildew inhibitors, wetting agents, antioxidants plasticizers, insecticides, adhesives, film-forming materials, &c.  The coating-compositions may be used for treating impervious and pervious surfaces, including textiles.  Treated rayon tyre cord adheres more readily to rubber, treated regenerated cellulose sheets show improved adherence of printing-inks and lacquers; and other compositions may be used as waterproof glues for veneers; an emulsion of a wax, a fixing agent such aluminium acetate having the product of the invention as emulsifying agent may be used for sizing and waterproofing fabrics and for affixing acid dyes to paper.  The products, with or without a fixing agent may be used as a size for paper, especially as a beater-size for chalk-filled paper; and a composition containing an aqueous dispersion of titanium oxide and/or other solid (which may be a mildew-preventive such as salicylanilide), a wetting agent a softener, and a product of the invention as dispersion agent may be used for sizing and delustring fabrics.ALSO:Protein derivatives are made by reacting protein with a lower aliphatic aldehyde or ketone and a primary or secondary amine containing less than 9 car