Polyalkane imides based on 3,3′,4,4′‐diphenyloxidetetracarboxylic, pyromellitic and 1,4,5,8‐naphthalenetetracaboxylic acids, and aliphatic diamines containing 4, 6, 8, 10, or 12 methylene groups have been studied. Relations governing the effect of structure on solubility, heat resistance, density, and crystallizability have been established. Conformation analysis has been carried out and models of the macromolecules have been constructed. The morphology of the crystalline polymers has been studied. For the polymers of the given class, crystallization capability is shown to be associated with the conformational flexibility of the macromolecular unit determining a given acid moiety by the number of methylene groups in the diamine unit.
The influence of the reactivity of the starting compounds and reaction conditions on the formation of the macromolecules of copolymers has been investigated for a nonequilibrium copolycondensation in solution by acceptor‐catalytic polyesterification. In the nonequilibrium copolycondensation in solution, copolymers with different distributions of units may be formed, depending on various factors. Introduction of all amounts of acid chloride (intermonomer) in the beginning of the nonequilibrium copolycondensation leads to the formation of copolymers with statistical distribution of the units independent of the difference in reactivity of the comonomers used. For synthesis of copolymers with a block structure by one‐stage nonequilibrium polycondensation in solution the initial comonomers must have different reactivities (r ≠ 1) and the rate of intermonomer introduction must be lower than that of its reaction with the more reactive comonomer. On varying the above factors, block copolymers with different lengths of block segments may be obtained.
Copolyimides, their microstructure being determined by the method of synthesis, were prepared by copolycondensation of 4,4'-oxydiphthalic anhydride (1 a), 4,4'-carbonyldiphthalic anhydride (1 b), or 1,8 : 4,5-naphthalenetetracarboxylic anhydride with a mixture of two diamines, hexa-, octa-, or dodecamethylene diamine (5 a, 6a, 7a) and cardo-diamines 9,9-bis(4'-aminopheny1)fluorene (3 a) and 3,3-bis(4'-aminophenyl)phthalide (4) or two aromatic diamines, 4,4'-oxydianiline (9) and 2,2-bis(4-aminophenyI)hexafluoropropane (8), at various mole ratios of the comonomers. Blockcopolyimides with five-membered imide cycles were formed by catalytic imidization of the intermediate polymers prepared by addition of the solid dianhydride to a solution of the mixture of the two diamines, whereas the thermal cyclization of such polymers and the one-step high-temperature synthesis led to random copolyimides. The thermal and mechanical properties of the copolyimides with various microstructure and their solubility in organic solvents were compared. *) Cardo groups (cardo = loop) are those incorporated into the main polymer chain with one atom which is a part of a cyclic system. Such groups are derived from phthalide, phthalimidine, fluorene, anthrone etc. They endow a polymer with very specific properties, like enhanced thermostability, excellent solubility etc. Makromol. Chem. 184, No. 2, February 1983 0025-1 16)83/$03.00 l a : R = O b: R = C O 2 gjg RHN ' ' NHR 3 a : R = H b : R = SYCH,), 4 8 9 Experimental PartThe initial monomers used and the methods of their purification are presented in Tab. 1. N,N'-bis(trimethylsily1)hexamethylenediamine (5 b) and N, N'-bis(trimethylsi1yI)octamethyle-nediamine (6b) were synthesized according to the known method5). N,N'-Bis(trimethylsilyl/dodecamethylenediamine (7 b):In a one-necked 100 ml flask were placed 20 g of dodecamethylenediamine (7 a) and then 50 ml of diethylaminotrimethylsilane '). The reaction mixture was stirred and heated for 3 h at 120°C (on a silicone bath) in argon atmosphere evaporating diethylamine, which was condensed in a trap cooled with solid CO,/acetone. After diethylamine evolution has ceased the reaction mixture was cooled and excess diethylaminotrimethylsilane was distilled off at 80°C in the vacuum of a water pump.The reaction mixture was then evacuated (residual pressure of 1 -4 mbar) at 90 -100 "C for 4 h and the resulting product was distilled at 150-151 "C/O,Ol mbar. Yield: 68%.C18H,N2Si2 (344,7) Calc. Si 15,96, 16,05 9,9-Bis(4'-trimethylsilyIaminophenyl)fluorene (3 b): In a one-necked 100 ml flask were placed 3,48 g of 9,9-bis-(4-aminophenyl)fluorene (3a), then 50 ml of chlorobenzene. The mixture was
Ncw soluble m-carborane-containing polymeric SCHIFF bases are prepared by polycondensation of m-carboranylenediamine, 1,7-bis(4-aminophenylcarboxy)-m-carborane, and 1,7-bis(4-aminophenylamido)-m-carborane with different dialdehydes in solution. Optimum conditions for polymer synthesis are found. The structure of the resulting polymers is confirmed by the synthesis of model compounds not described earlier, IR spectroscopy, and elemental analysis data. Some properties of m-carborane-containing polymeric SCHIFF bases and their model compounds have been studied. Neue na-Carboran enthaltende polymere Schiffsche BasenNeue liisliche, m-Carboran enthaltende polymere SCHIFFsche Basen wurden durch Polykondensation von m-Carboranylendiamin, 1,7-Bis-(4-aminophenylcarboxy)-m-carboran und 1,7-Bis-(4-aminophenylamido)-m-carboran mit unterschiedlichen Dialdehyden in Losung hergestellt. Die optimalen Bedingungen fur die Synthese der Polymere wurden ermittelt. Die Struktur der erhaltenen Polymere wurde durch die Synthese von bisher nicht beschriebenen Modellverbindungen, durch IR-Spektroskopie und durch Elementaranalyse bestatigt. Einige Eigenschaften der m-Carboran enthaltenden polymeren SCHIFFschen Basen und ihrer Modellverbindungen wurden untersucht. Hoebte m -~a p 6 o p a n c o d e p~a q u e noAuuu$$oebce ocnoeafimHOBbIe PaCTBOPMMbIe M-Kap6OpaHCOnepxtanHe IIOJIHIUH@@OBbIe OCHOBaHHR IIOJIyqeHbI IIOJIIXHOHAqeIICaqHet M-Kap6OpaHAneHAAaMHHa, 1,7-6HC-( 4-aMIIHO-@C!HHJIKap6OKCH)-M-Ka~6OpaHa II 1,7-6AC-(4-aMIIHO@eHHnaMHAO)-M-Kap6OpaHa C pa3JIAYHbIMII AHaJIbAeI'HAaMH B paCTBOpe. OCy~eCTBJIeH non6op OIITHMaJIbHbIX J'CJIOBHm CEIHTe3a IIOJIAM~?pOB. CTpOeHHe IIOJIyqeHHbIX IIOJIHMepOB IIOnTBePHcAeHO CHHTe30M PaHee HeOIIHCaHHbIX MOAeJlbHbIX COeAH-HeHAa, AaHHbIMII u~-CIIeKTpOCKOIIHH A 3JIeMeHTHOrO aHaJIII3a. u3YqeHbI HeKOTOpbIe CBOPCTBa M-Kap6OpaHCOJ(ep-XawHX IIOJIAIIIH@@OBbIX OCHOBaHHa A HX MOAeJIbHbIX COeAHHeHHfi.
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