脂肪族ジアミンの合成に関する研究(第1報) : テトラヒドロフランよりエーテル型,チオエーテル型ジアミンの合成とそのポリ尿素
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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/cm<SUP>2</SUP> 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(CH<SUB>2</SUB>)<SUB>4</SUB>[O(CH<SUP>2</SUP>)<SUB>8</SUB>]<SUB>n</SUB>O(CH<SUB>2</SUB>)<SUB>4</SUB>OH. 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/mm<SUP>2</SUP>, 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.
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