Patent GB-777398-A (GB)
Title: Linear amide-ester polymers
IPC: C08G63/685
Filed: 1955-04-21
Abstract: Polyesteramides of the formula <FORM:0777398/IV(a)/1> or <FORM:0777398/IV(a)/2> are prepared by reacting dicarboxylic acids with either a monoamide diol or a diamide diol.  These glycols may be prepared by reacting an omega lactone with an aminoalcohol or a diamine. In the above formul  R is a divalent saturated hydrocarbon chain of 2 to 11 carbon atoms or a saturated hydrocarbon chain containing an ether or thioether link and having from 2 to 9 carbon atoms, or an arylene group or a divalent saturated hydrocarbon chain containing one or more arylene groups. R1 and R111 are saturated hydrocarbon chains of at least 4 carbon atoms and R11 is a saturated hydrocarbon chain of at least two carbon atoms.  Heptafluorobutyric acid may be used as polymerization catalyst and the reaction mix may contain small proportions of the omega lactone used in the amide diol synthesis to repress breakdown of the amide diol.  The lactone does not react in the first stage of polymerization which consists in heating at 100-300 DEG  C. at a pressure between 30 mm. Hg and one atmosphere for 9-24 hours, and is removed in the second stage which consists in heating at 100-300 DEG  C. at a pressure less than 3 mm. Hg for 5-24 hours until a polymer having a reduced viscosity of between 0.4 and 0.9 is obtained.  The polymers form films and fibres and may be rubbery.  Seven examples are given in which polymers are obtained from (1) and (2) terephthalic acid and N,N1-di(6-hydroxy-caproyl)-hexamethylene diamine; (3) adipic acid and N,N1 - di(6 - hydroxycaproyl) - hexamethylene diamine; (4) adipic acid and N,N1-di-(6-hydroxycaproyl) ethylene diamine; (5) adipic acid and N,N1-di-(5-hydroxyvaleryl) hexamethylene diamine; (6) adipic acid and N-hydroxyethyl, 6-hydroxycaproamide; (7) thiodipropionic acid and N,N1-di-(6-hydroxycaproyl) hexamethylene diamine.ALSO:Hydroxyamides having the formula HOR1(CONHR11)nNHCOR111OH where n is 0 or 1, R11 is a divalent saturated hydrocarbon chain containing at least two carbon atoms, an arylene group or a divalent hydrocarbon chain which contains, internally, an arylene group, R111 is an aliphatic divalent saturated hydrocarbon chain containing four to ten carbon atoms, and R1 when n is 0 is a divalent saturated aliphatic hydrocarbon chain containing two to ten carbon atoms, an arylene group or a divalent hydrocarbon chain which contains, internally, an arylene group, and when n is 1 is the same as R111, are made by reacting an omega lactone with an omega hydroxy primary amine or with a diprimary amine.  The limitation on R111 being at least four carbons in length is due to the instability of the hydroxyamides in which the radicals R111 have three or fewer carbon atoms, the corresponding lactone being preferentially formed.  Excess lactone is employed in the reaction to repress any tendency to reversion.  The Specification refers to the following monoamide diols: N-hydroxyethyl, 6.hydroxycaproamide; N-3.hydroxypropyl, 5.hydroxyvaleramide; N - 4.hydroxybutyl, 5.hydroxyvaleramide; N - 4 . hydroxybutyl, 5 . hydroxy, 3. methylvaleramide; N - 8 . hydroxyoctyl, 10. hydroxydecanoamide; N - 10 . hydroxydecyl, 5 . hydroxyvaleramide; N - p . hydroxyxylyl, 6.hydroxycaproamide; and the following diamide diols: N.N1 - di - (5.hydroxyvaleryl) ethylenediamine; N.N1 - di - (5.hydroxy, 3. methylvalery) hexamethylenediamine; N.N1-di - (6.hydroxycaproyl) octamethylenediamine; N.N1 - di - (5.hydroxyvaleryl) decamethylenediamine; N.N1 - di - (5.hydroxyvaleryl) p.-phenylenediamine; N.N1 - di - (10.hydroxy - decanoyl) p.p1.biphenylenediamine; N.N1 - di-(6.hydroxycaproyl) 2.6 . naphthalenediamine.  The amide diols are used for the production of polyester-amides (see Group IV (a)).  In examples, the following compounds are used: N.N1-di-(6 . hydroxycaproyl) hexamethylenediamine; N.N1-di-(6 . hydroxycaproyl) ethylene diamine; N.N1-di-(5 . hydroxyvaleryl) hexamethylenediamine; N-hydroxyethyl, 6.hydroxycaproamide.