Patent GB-561108-A (GB)
Title: Manufacture of polyesteramides
IPC: C08G69/44
Filed: 1942-07-01
Abstract: Polyesteramides are made by heating a mixture comprising bifunctional polyamide forming and bifunctional polyester forming reactants the minimum or essential ingredients of the mixture being a monoaminomonohydric alcohol, a dibasic carboxylic acid and a dihydric alcohol, the proportion of the monoaminomonohydric alcohol being not less than 5.0 molar per cent based on the other reactants.  The mixture may also contain diamines, amino acids or hydroxy acids.  It should contain substantially equimolecular proportions of the ester-forming groups as well as of the amide-forming groups, but a small excess of dihydric alcohol may be used.  The preferred amino alcohol has less than 4 atoms between the amino and hydroxyl groups. Suitable amino alcohols are, for example, ethanolamine, 3 - aminopropanol, 4 - aminobutanol, 6 - aminohexanol, 10 - aminodecanol, p - NH2CH2CH4 CH2OH or aminoalcohols of the formula <FORM:0561108/IV/1> when x and y are integers, R1 is a monovalent hydrocarbon radical and R11 is hydrogen or a monovalent hydrocarbon radical.  The dibasic acid may be of the formula COOH-R-COOH where R is a saturated divalent hydrocarbon radical with at least 4 C atoms. The preferred dibasic carboxylic acid has a radical length, as defined in Specification 461,237, of at least 6. Terephthalic acid and HOOC.CH2CH2CH2S.CH2 CH2CH2COOH may be used.  If the amino and hydroxyl group of the aminoalcohol are separated by more than 4 atoms, the chain separating the COOH groups of the dibasic acid may be shorter, and malonic or glutaric acid may be used.  Suitable dihydric alcohols are trimethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, p-HOCH2-C6H4-CH2OH or HOCH2CH2-S-CH2CH2OH.  Suitable diamines which may be added to the reaction mixture are ethylenediamine, hexamethylenediamine, 3-methyl hexamethylene diamine, decamethylenediamine, m - phenylenediamine, or 3 : 31-diaminodipropyl ether.  Suitable hydroxy acids are w-hydroxycaproic acid, w-hydroxydecanoic acid or w-hydroxymyristic acid.  Examples of amino acids which may be added are 6-aminocaproic acid, caprolactam, 9 - aminononanoic acid, 11 - aminoundecanoic acid or 12-aminostearic acid.  Any of the above substances may be present in the reaction mixture as amide-forming or ester-forming derivatives.  The reaction is preferably performed in two stages, the first at 150-180 DEG  C. for at least 2 hours and the second at 180-250 DEG  C. preferably under reduced pressure.  Water may be present during the first stage to give a homogeneous reaction mixture and to decrease frothing.  In the second stage nitrogen or carbon dioxide may be conducted over or through the mixture to prevent oxidation and aid removal of water. Water may also be removed azeotropically with xylene or toluene. The products may be oily, wax-like or capable of forming fibres. They are soluble in mixed solvents such as methanol and chloroform and may be used as film-forming materials or for coating or impregnating wood, cloth, leather or paper.  Examples describe the preparation of polyesteramides from ethanolamine, pentaglycol and sebacic acid; from ethanolamine, ethylene glycol, and sebacic acid; and from ethanolamine, ethylene glycol and adipic acid.  Samples have been furnished under Sect. 2 (5) of polyesteramides prepared from (1) ethanolamine, ethylene glycol, adipic acid and hexamethylene diammonium adipate, (2) pentanolamine, ethylene glycol and adipic acid, (3) ethanolamine, ethylene glycol, adipic acid and caprolactam, (4) ethanolamine, ethylene glycol, adipic acid and glycollic acid, (5) ethanolamine, ethylene glycol and methylene-bis-thioglycollic acid, (6) ethanolamine, ethylene glycol, adipic acid and terephthalic acid and (7) 2-amino-1-propanol, ethylene glycol and adipic acid. Specifications 461,237, 535,335, 535,421 and 553,733 are referred to.