Patent GB-341447-A (GB)
Title: Process for producing condensation products from polybasic acids and polyhydric alcohols
IPC: C08G63/12
Filed: 1929-10-11
Abstract: Coating compositions which yield flexible films contain ester condensation products obtained from polyhydric alcohols such as glycerol and aliphatic polybasic acids which possess more than six carbon atoms linked together in a normal straight chain, especially sebacic acid, said polybasic acids being used separately or in mixtures thereof and in the absence of a monohydric alcohol.  The use of pimelic, suberic, and azelaic acids is also referred to, and it is stated that the condensation takes place in three stages to form, "A" a thin syrupy initial condensation product, soluble in acetone, an intermediate product "B" which is a soft, flexible, tacky, rubbery mass, soluble in acetone or ethyl acetate, but insoluble in benzol, and a final product, "C," which is a soft, flexible, elastic and very tough solid, insoluble in the common organic solvents.  According to the Example, 1 and 1,5 molecular equivalents by weight of glycerol and sebacic acid respectively are heated at 165-170 DEG  C. until a sample sets to a firm jelly on cooling.  Heating for 4,5 hours completes the first stage and for 4,75 hours completes the second stage, further heating for half-an-hour yielding the final product. Instead of glycerol, other polyhydric alcohols may be used, such as polyglycerol, diethylene glycol, triethylene glycol, and ethylene glycol.  The B and C condensation products may be toughened by dissolving them in natural and synthetic resins.  Acidic resin such as colophony may take part in the condensation.  According to an example, 30 parts by weight of colophony, 15 parts of sebacic acid, and 15 parts of glycerol, by weight, are heated rapidly to 195-200 DEG  C. with stirring, and thereafter the temperature is increased to 250-260 DEG  C. the final product being soluble in benzol.  The soluble products obtained when using the polybasic acids specified are miscible with nitrocellulose in butyl acetate-toluol solution to give transparent, flexible and very elastic films.  Such films are stated to be particularly useful for coatings for porous substances such as leather woven fabrics, paper, and rubber. Instead of nitrocellulose, cellulose acetate may be employed, and softening agents such as castor oil and pigments and plasticizers may be added. The proportions of the ingredients may be varied, such as from 150 to 500 per cent of the condensation product to the weight of dry nitrocellulose employed.  In some cases rubber may be coated first with the condensation product and subsequently with a film of nitrocellulose.  Tough flexible films may also be formed from a solution containing a phenol-formaldehyde resin and one of the previously specified condensation products, stated to be useful for coating oil-storage tanks.  For this purpose 100 parts of a soluble "Novolac" resin or reactive phenolaldehyde resin is dissolved in 200 parts of alcohol and mixed with 50 parts by weight of the soluble, rubbery condensation product prepared by heating glycerol with sebacic acid.  Other resins which may be employed similarly are shellac, cresol-formaldehyde resins, ketone-formaldehyde resins, formaldehyde-urea resins, and the condensation products of phenol with furfurol.ALSO:Ester condensation products are obtained from polyhydric alcohols such as glycerol and aliphatic polybasic acids which possess more than six carbon atoms linked together in a normal straight chain, especially sebacic acid, said polybasic acids being used separately or in mixtures thereof and in the absence of a monohydric alcohol.  The use of pimelic, suberic, and azelaic acids is also referred to, and it is stated that the condensation takes place in three stages to form, " A " a thin syrupy initial condensation product, soluble in acetone, an intermediate product " B " which is a soft, flexible, tacky, rubbery mass, soluble in acetone or ethyl acetate, but insoluble in benzol, and a final product, " C " which is soft, flexible, elastic and very tough solid, insoluble in the common organic solvents.  According to the Example, 1 and 1,5 molecular equivalents by weight of glycerol and sebacic acid respectively are heated at 165-170 DEG  C. until a sample sets to a firm jelly on cooling.  Heating for 4,5 hours completes the first stage and for 4,75 hours completes the second stage, further heating for half-an-hour yielding the final product.  At higher temperatures such as 190-200 DEG  C. the reaction is difficult to control.  The soluble products obtained when using the polybasic acids specified are miscible with nitrocellulose in butyl acetate-totuol solution to give transparent, flexible and very elastic films.  Such films are stated to be particularly useful for coatings for porous substances such as leather woven fabrics, paper, and rubber, and for preparing flexible photographic films, and for this purpose one part of the soluble, rubber-like condensation product prepared according to the above Example is dissolved in butyl acetate and mixed with a solution of an equal weight nitrocellulose.  Instead of nitrocellulose, cellulose acetate may be employed, and softening agents such as castor oil and pigments and plasticizers may be added.  The proportions of the ingredients may be varied, such as from 150 to 500 per cent of the condensation product to the weight of dry nitrocellulose employed, particularly for application to rubber surfaces.  In some cases the rubber may be coated first with the condensation product and subsequently with a film of nitrocellulose. Instead of glycerol, other polyhydric alcohols may be used, such as polyglycerol, diethylene glycol, triethylene glycol and ethylene glycol.  The soluble intermediate condensation product " B " may be hardened by dissolving in natural and synthetic resins, or the resin acids such as colophony may take part in the condensation.  According to an example, 30 parts by weight of colophony, 15 parts of sebacic acid, and 5 parts of glycerol, by weight, are heated rapidly to 195-200 DEG  C. with stirring and thereafter the temperature is increased to 250-260 DEG  C., the final product being soluble in benzol.  Tough flexible films may also be formed from a solution containing a phenol-formaldehyde resin and one of the previously specified condensation products, stated to be useful for coating oil storage tanks.  For this purpose 100 parts of a soluble Navolock resin or reactive phenol-aldehyde resin is dissolved in 200 parts of alcohol and mixed with 50 parts by weight of the soluble, rubbery condensation product prepared by heating glycerol with sebacic acid. Other resins which may be employed similarly are shellac, cresol-formaldehyde resins, ketone - formaldehyde resins, formaldehyde - urea resins, and the condensation products of phenol with furfurol.  The resin components may, alternatively, be powdered and mixed with the rubbery, viscous condensation products; the pasty mass or impregnated powder so obtained may be used for moulding objects.ALSO:Containing natural and artificial resins.-For moulding objects the pasty mass or impregnated powder is used obtained by mixing powdered synthetic resins with the ester condensation products obtained from polyhydric alcohols such as glycerol and aliphatic polybasic acids which possess more than six carbon atoms linked together in a normal straight chain, especially sebacic acid, said polybasic acids being used separately or in mixtures thereof and in the absence of a monohydric alcohol.  The use of pimelic, suberic, and azelaic acids is also referred to, and it is stated that the condensation takes place in three stages to form, "A" a thin syrupy initial condensation product, soluble in acetone, an intermediate product "B" which is a soft, flexible, tacky, rubbery mass, soluble in acetone or ethyl acetate, but insoluble in benzol, and a final product, "C," which is soft, flexible, elastic and very tough solid, insoluble in the common organic solvents.  According to the Example, 1 and 1,5 molecular equivalents by weight of glycerol and sebacic acid respectively are heated at 165-170 DEG  C. until a sample sets to a firm jelly on cooling.  Heating for 4,5 hours completes the first stage and for 4,75 hours completes the second stage, further heating for half-an-hour yielding the final product.  At higher temperatures such as 190-200 DEG  C. the reaction is difficult to control.  The soluble products obtained when using the polybasic acids specified are miscible with nitrocellulose in butyl acetate-toeuol solution to give transparent, flexible and very elastic films.  Instead of glycerol, other polyhydric alcohols may be used, such as polygycerol, diethylene glycol, triethylene glycol and ethylene glycol.  The soluble intermediate condensation product "B" may be hardened by dissolving in natural and synthetic resins or the resin acids such as colophony may take part in the condensation. According to an example, 30 parts by weight of colophony, 15 parts of sebacic acid, and 5 parts of glycerol, by weight, are heated rapidly to 195-200 DEG  C. with stirring and thereafter the temperature is increased to 250-260 DEG  C. the final product being soluble in benzol.  Tough flexible films may also be formed from a solution containing a phenol-formaldehyde resin and one of the previously specified condensation products.  For this purpose 100 parts of a soluble navolack resin or reactive phenol-aldehyde resin is dissolved in 200 parts of alcohol and mixed with 50 parts by weight of the soluble, rubbery condensation product prepared by heating glycerol with sebacic acid.  Other resins which may be employed similarly are shellac, cresol-formaldehyde resins, ketone-formaldehyde resins, formaldehyde-urea resins, and the condensation products of phenol with furfurol.  The resin components may, alternatively, be powdered and mixed with the rubbery, viscous condensation products; the pasty mass or impregnated powd