Cationic polyelectrolytes. III. Nitrile‐group reaction of macromolecular compounds with N,N‐dialkylaminoalkylamines

Abstract

SynopsisThe chemical reaction in aqueous medium of polyacrylonitrile and acrylonitrile-vinyl acetate copolymer using asymmetrical diamines of H2N-(CH2),-NR2 ( m = 2,3) structure was studied. It was found that the nitrile group is modified to an dialkylaminoalkylacrylamide group; also determined were the reaction conditions required to obtain the highest degree of chemical transformation of the nitrile groups. All modified compounds were characterized by analytical spectroscopy (IR and 'H NMR) and by rheological methods. It was also established that glutaronitrile can be used as a low-molecular-weight model to study the chemical transformation of nitrile groups in polyacrylonitrile and related polymers. P-, and y-dinitriles only, where there exists the possibility of a ring-shaped intermediate.7 However, the uncatalyzed reaction also occurs for other nitrile compounds if the nitrile group is activated by certain functional groups.s Also reported is the reaction of PAN with diamines of H2N-(CH2)m-NH2 ( m = 2,3) structure, which leads to poly(viny1amidines) when performed with a catalyst in anhydrous media.g This paper described the reaction in water of PAN and its copolymers with asymmetrical diamines of H2N-(CH2),-NR2 ( m = 2,3) structure. The reaction takes place without a catalyst, perhaps because of the appearance of imide rings during intermediate reaction steps. The macromolecular compounds DRAGAN ET AL studied were PAN and a technical acrylonitrile (9&95%)-vinyl acetate (510%) copolymer (AN-VAc), as fibers.Chemical reactions were investigated in the absence of organic solvents, at atmospheric pressure. EXPERIMENTALThe acrylonitrile was previously distilled. PAN was prepared by polymerization in water using a redox K$320s/K&05 initiator system at 60°C. The polymerization time was about 70 min. Polymer was poured into eight volumes of hot water, then it was filtrated and the precipitate washed with hot water and methanol.The polymer was dried, dissolved into N,N-dimethylformamide, and precipitated in methanol. The average molecular weight was viscosimetrically measured in DMF at 25OC, using the equationlo [q] = 2.43 x 10-4 x Z;0.75 PAN, prepared by us, was of M , = 100,400. AN-VAc fibers were washed with methanol, dried, and cut in small pieces (2-3 cm).

Organic ion exchangers as beads. Synthesis, characterization and applications

“…Hofmann degradation of the amide groups contained in a crosslinked copolymer of acrylamide (AA), according to the method employed by Tanaka and Senju for the preparation of poly(vinylamine) from polyacrylamide, 20 has been already used to prepare WBAEs with vinylamine units. 21 WBAEs with aminoethylacrylamide units were generated in this study by the aminolysis-hydrolysis reaction with 1,2-diaminoethane (EDA) of the nitrile groups, contained in some porous AN-DVB copolymers, according to the method previously established for polyacrylonitrile (PAN) 22 and applied by others. 23 A large number of studies about the synthesis and characterization of the selective chelating ion exchangers with wide applicability in the removal of toxic metal and complex ions from industrial effluents, as well as in metal ion recovery processes, were lately achieved.…”

Synthesis and Characterization of Novel Organic/Inorganic Hybrid Material with Short Peptide Brushes Generated on the Surface

“…The PAEA was synthesized by an aminolysis−hydrolysis reaction with 1,2-diaminoethane, converting the nitrile groups of polyacrylonitrile into the amino-terminated structure shown in Chart . The synthesis was described in detail in a previous paper . BTCDA, N , N ‘-dicyclohexyl carbodiimide (DCC, Merck, Darmstadt, Germany), and boc- S -benzyl- l -cysteine (Fluka, Germany) were used as received.…”

“…The synthesis was described in detail in a previous paper. 22 BTCDA, N,N′-dicyclohexyl carbodiimide (DCC, Merck, Darmstadt, Germany), and boc-S-benzyl-L-cysteine (Fluka, Germany) were used as received. The structures of all reagents are summarized in Chart 1.…”

Thermochemically induced binding of methyl orange to polycations containing primary amine groups

“…Poly(β‐aminoethylene acrylamide) (PAEA) was synthesized by the aminolysis–hydrolysis reaction of polyacrylonitrile with ethylenediamine according to a method previously presented 44. PAEAH was synthesized by the addition of 1.2 mol of HCl/mol of the PAEA repeat unit at 80 °C for 90 min.…”