Patent GB-639733-A (GB)
Title: Improvements relating to ethers containing a saturated carbon ring
IPC: C08G69/26
Filed: 1947-08-22
Abstract: 1,4-Bis-(3-aminopropoxy)-cyclohexane or a salt thereof heated with a dibasic carboxylic acid, especially a dicarboxylic acid, gives polyamides.  Suitable acids are adipic, sebacic, terephthalic, bis-(p-carboxyphenoxy)-alkanes and the corresponding thio-ether acids, 2,21-bis-(p-carboxyphenoxy)-diethyl ether and similar derivatives of other dialkyl ethers and thio-ethers, hydroquinone diacetic and di-p-benzoic acids, bis-(p-carboxyphenyl) derivatives of alkanes, p,p1-dicarboxydiphenyl naphthalene 1 : 5,2 : 6, and 2 : 7-dicarboxylic acids, 1,4-bis-(p-carboxyphenoxymethyl)-benzene, p,p1-dicarboxydiphenyl ether and thio-ether.  Dicarboxylic acids of less than 6 carbon atoms such as oxalic, and also carbonic acid can be used.  Polymerization may be in stages, e.g. first at atmospheric pressure or above, and finally below 5, preferably 2 mm. or less when fibre-forming products are required. Such products preferably result from acids wherein the carboxyl groups are separated by a chain of at least 4 atoms.  Mixtures of dibasic acids may be used, and other diamines such as hexa- or tetra-methylene diamine incorporated.  The high linear polymers may be used in the manufacture of filaments, yarns, and other shaped products, and moulding compositions. Insoluble, infusible resins are produced by reacting the ethers containing amino, carboxyl or esterified carboxyl end groups with compounds containing 3 or more groups reactive therewith.  Examples describe the condensation with adipic acid, diethyl oxalate, terephthalic acid, 1,2-bis-(p-carboxyphenoxy)-ethane, 1,4 - bis - (p - carboxyphenoxy)-butane, 1,6 - bis - (p - carboxyphenoxy) - cyclohexane, 2,21 - bis - (p - carboxyphenoxy)-diethyl ether and hydroquinone diacetic acid, the products being heated to melting point, or with m-cresol under nitrogen to form high polymers capable of forming fibres.ALSO:Acrylonitrile and quinitol in a molar ratio of at least 2 : 1, e.g. 4-12, and especially 5-8 : 1, are heated in the presence of a basic substance to yield 1,4-bis-(2-cyanoethoxy)-cyclohexane. An inhibitor of polymerization such as quinol may be present.  An alkali metal alkoxide, especially sodium or potassium ethoxide, in the corresponding alcohol is preferably used as the basic catalyst.  After refluxing for several hours, the product can be separated by cooling and filtering. Unchanged acrylonitrile may be recovered by distillation from the filtrate, the residue being distilled under reduced pressure and the distillate cooled to separate quinitol.  The bis - cyanoethoxy - cyclohexane may be hydrogenated, for example in methanol or dioxane, and preferably in presence of ammonia, using a nickel catalyst at 50-150 DEG  C. and 50-300 atmos., to give 1,4 - bis - (3 - aminopropoxy)-cyclohexane.  It may also be hydrolysed to the corresponding dicarboxylic acid by warming with excess of hydrochloric acid not substantially above 70 DEG  C., e.g. at about 50 DEG  C., for some days.  Alcoholysis similarly yields the dicarboxylic ester.  Thus, boiling with excess of ethanol and with water while passing hydrogen chloride gives the diethyl ester. The di-isopropyl ester is prepared in similar manner. Alternatively, the free acid may be heated with the alcohol and an esterification catalyst or converted into its dimethyl ester with dimethyl sulphate. Resinous condensation products; polyamides.  1,4 - Bis - (3 - aminopropoxy) - cyclohexane or a salt thereof heated with a dibasic carboxylic acid, especially a dicarboxylic acid, gives polyamides (see Group IV (a)).  The high linear polymers may be used in the manufacture of filaments, yarns and other shaped products, and moulding compositions.  Insoluble, infusible resins are produced by reacting the ethers containing amino, carboxyl or esterified carboxyl end groups with compounds containing 3 or more groups reactive therewith.  Examples describe the preparation of the cyano-ether, its conversion to the dicarboxylic acid and ester, hydrogenation to the diamine, and condensation of the latter with dicarboxylic acids or esters, the products being heated to melting point, or with m-cresol under nitrogen to form high polymers capable of forming fibres.