Patent GB-660111-A (GB)
Title: Fluorinated polyamides
IPC: C08G69/42
Filed: 1947-11-26
Abstract: Linear polyamides containing fluorine are formed by reacting dicarboxylic acid derivatives of formula Y(CX12)nY (where X1 is hydrogen or fluorine, and Y is either a COCl or COOR group, R is a lower alkyl radical and n is 1 to 5) with diamines of the formula H2N.CH2.(CX2)mCH2.NH2 (where m is 0 to 4 and X is hydrogen or fluorine), the reactants being selected so that at least one of X and X1 is fluorine.  From hexamethylene diamine and perfluoro-dicarboxylic acid derivatives, low molecular products are obtained by heating at about 100-125 DEG  C., which on heating at 200 DEG  C., yield fibre-forming high polymers.  If a fluorinated amine, e.g. octa-fluoro-1, 6-hexane diamine, and a non-fluorinated carboxylic acid derivative are reacted, products of molecular weight below 10,000 result, and if both reactants are fluorinated, e.g. octafluoro-1, 6-hexane diamine and octafluoro adipyl chloride, waxy solids of still lower molecular weight result.  Filaments may be produced from the melt of the high polymers or by wet- or dry-spinning, and may then be cold drawn.  Examples (1) and (2) describe heating the reactants at 100-140 DEG  C. in a closed vessel to form a low polymer, heating the product in an open vessel at 80-100 DEG  C. to remove by-products, and then heating at 205-215 DEG C., first in an inert atmosphere and then at reduced pressures to form the high polymers.  Reactants employed are hexamethylene diamine and (1) diethyl octa-fluoroadipate, (2) diethyl hexafluoro glutarate. In further examples are reacted 2,2,3,3,4,4,5,5, octafluoro-1,6-hexane-diamine, and (3) diethyl octafluoro-adipate, (4) diethyl adipate, and (5) adipyl chloride, the heating at 205-215 DEG  C. being omitted.  The products are insoluble in most organic solvents but soluble in hot dimethyl formamide.  Instead of the diethyl ester, the methyl, propyl, isopropyl, allyl, butyl, butenyl, isobutyl, amyl, pentenyl, hexyl or hexenyl diester may be used. Alternative amines are ethylene diamine, propylene diamine, 1,4-butane diamine, pentamethylene diamine, difluoro-1, 3-propane diamine, tetrafluoro-1, 4-butane diamine, and hexafluoro-1, 5-pentane diamine.  Diamines corresponding to the perfluoro-dicarboxylic acids may be prepared by reacting a diester of the acid with anhydrous gaseous ammonia to form the diamide, converting it to the corresponding nitrile, reacting the nitrile with an acyl anhydride to obtain the diacyl derivative of the diamine and forming a salt thereof, such as the sulphate, from which the free diamine is recovered.ALSO:Fluorinated dicarboxylic acid derivatives of the formula Y(CF2)n Y, where Y is the group -COCl or -COOR, R being an alkyl radical containing one to eight carbon atoms or hydrogen, and n an integer from 1 to 5, are prepared by fluorinating perchlorocycloalkylenes to effect fluorination on all nuclear carbon atoms except the double-bonded carbon atoms, and oxidizing the alkene to the corresponding perfluoro-dicarboxylic acid.  The product is converted to the diester by reaction with an alcohol, or converted to the acyl chloride by reaction with, e.g. phosphorus trichloride. Diamines corresponding to the acids may be prepared by reacting a diester of the perfluoro carboxylic acid with anhydrous gaseous ammonia to form the diamide of the acid, converting the amide to the nitrile, reacting the nitrile with an acyl anhydride in the presence of a catalyst and in an atmosphere of hydrogen to form the diacyl derivative of the diamine, forming a salt, e.g. the sulphate thereof, and recovering the free diamine from the salt. Mentioned are diethyl octafluoradipate, diethyl hexafluoroglutarate, octafluoro - 1,6 - hexane - diamine, difluoro-1,3-propane diamine, tetrafluoro-1,4-butane diamine, and hexafluoro-1,5-pentane diamine. Radicals which R may represent include methyl, propyl, isopropyl, allyl, butyl, butenyl, isobutyl, amyl, pentenyl, hexyl and hexenyl radicals.