Conditions for syntheses of bis (4-aminobutyl) ether (BABE), bis(5-aminopentyl) ether (BAPE), bis (5-aminopentyl) thioether (BAPSE) and suberic acid by use of tetrahydrofuran (THF) as a starting material was investigated. Also, the syntheses of polyureas were carried out by condensation-polymerization reaction of these diamines and urea and their properties were clarified. Synthesis of 1, 4-dichlorobutane (DCB) from THF was investigated by a combined use of 35% hydrochloric acid and concentrated sufuric acid, or zinc chloride and thionyl chloride, and the yield of DCB 81-86% and bis (4-chlorobutyl) ether (BCBE) 5-6% was obtained. Reaction of THF, thionyl chloride and concentrated sulfuric acid yielded 85% of BCBE but the formation of chlorinated products varied depending on the molar ratio of thionyl chloride added, and the formation of dichloropolybutoxybutane and 1, 4-bis (4-chlorobutoxy) butane increased when the molar ratio of thionyl chloride was small. The synthesis of BABE from BCBE gave 69% yield in ammonolysis method and 78% in potassium phthalimide method. Reaction of BCBE and sodium cyanide in anhydrous methanol-dimethylsulfoxide (DMSO) yielded 91% bis (4-cyanobutyl)-ether (BNBE). Its reductive amination caused easy breaking of ether linkage when the initial hydrog enation pressure was low at high temperature. Thus, the yield of 95% BAPE was obtained with initial hydrogenation pressure at 130-150 kg/cm2 and at around 80°C. Nitric acid oxi dation of Wurtz reaction product of BCBE with sodium suspension gave products containing mainly succinic acid and suberic acid. Then it is considered that the structure of Wurtz reaction product is close to HO(CH2)4[O(CH2)8]nO(CH2)4OH. δ-chlorovaleronitrile (CVN) from DCB and sodium cyanide was synthesised in 56% yield and his (4-cyanobutyl) thioether (BNBSE) from CVN and sodium sulfide was synthesised in 85% yield, from which BAPSF was obtained in 75% yield by sodium reduction. Condensation polymerization reaction takes place by heating of the diamines and urea, with the evolution of ammonia giving polyureas of good spinning property. The polyurea from BABE has the m, p. 216°C. and d. 1.16, the polyunea from BAPE has m.p, at 187°C, and d. 1.13, the polyurea from BAPSE has the m. p, at 205°C, and d, at 1.17. The fiber of each polymer has 3-4.5 g/d, elongation 20-28%, Young coefficient, 260-320 kg/mm2, good dyeing affinity and strong resistance against alkali but weak resistance against concentrated sulfuric acid. The properties of BABE polyurea fiber are close to 6 Nylon with the exception of dyeing affinity.
Reaction of ethylene glycol, water, ammonia and acrylonitrile yielded bis(β-cyanoethoxy)ethane-1, 2 (BCEOE), bis(β-cyanoethyl)ether (BCEE), and bis(β-cyanoethyl)imine (BCEI), from which bis(γ-aminopropoxy)ethane-1, 2, (BAPOE), bis(γ-aminopropyl)ether (BAPE), and imino-bis(γ-propylamine) (IBPA) weresyn-thesized by hydrogenation. Polyureas were synthesized from these diaminesandurea. Physical constants, such as b.p., d, nD and the yield of BCEOE, BCEE, BAPOE and BAPE showed some differences from the reference articles. The cause of these differences may be attributed to the bactthat these dinitriles are unstable against bases under heat and easily decomposed during the distillation andhyd rogenation, so its improvement was investigated. It was found that the thermal decomposition of dinitrile could be prevented by neutralization of crude nitrile to pH 7-7.5 and distillation after enough drying. Hydrogenation with the use of nickel or cobalt catalyst in the presence of ammonia or reduction with metallic sodium in liquid ammonia caused easy breaking of ether-carbon linkage. The yield was higher wilhout the additiion of baee The yield of IBPA from hydrogenation of AN was 80% even in the presence of base. By heating of BAPOE or BAPE and urea proceeded the condensationpolymerization reaction with the evolution of ammonia and gave polyurea of good spinning property. The former showed m.p. 150°c. and d204 1.14, and the latter showed m.p. 232°c and d204.18, the product from IBPA and urea gave a threedimension polymer with m.p. 182°c., having no spinning property.