Guanamine dendrimerization

A synthesis of dendrimers and hyperbranched polymers by using cycloaddition of cyanoguanidine to nitriles and cyanoethylation reaction is reported. Bo th reactions proceeded in the presence of a basic catalyst (alkaline hydrox ides and Triton B, respectively). The guanamine dendrimerization process ha s been carried out up to 4th generations ended with cyano or amine groups. Intermediates and product substances, as well as by-products were identifie d by FT-IR, H-1 and C-13 NMR, MS, FIB-MS, and elemental analysis. Hyperbran ched polymers were characterized by gel permeation choursomatography (GPC). Polyguanamine dendrimer (PGD) molecules exhibited expanded form in dimethy lacetamide solution and low polydispersity (1.12-1.26). Observed contractio n of the macromolecules was growing towards higher generations reaching an extreme at generation 4. The degree of branching of the products were withi n the range of 0.81-0.87 on the 0-1 scale. Decyanoethylation, hydrolysis, and intramolecular cyclization, as side reac tions, were observed on the cycloaddition steps of dendrimerization. Some m ain stream dendrimerization products, i.e., tetrakis [2-(2,4-diamino-1,3,5 -triazin-4-yl)ethyl]2,4-diamino-6-phenyl-1,3,5-triazine and 2,2,6,6-tetraki s[2-(2,4-diamino1,3,5 -triazin-6-yl)ethyl] cyclohexanone as well as by-prod ucts, i.e., 2,6,6-tris[2-(2,4-diamino-1,3,5-triazin-6-yl)ethyl] cyclohexano ne, 2,6,6-tris(2-cyanoethyl)cyclohexanone and a dilactam have been isolated as new compounds. Spectral data for (NNNN4)-N-2-N-2-N-4-tetrakis(2-cyanoet hyl)-6-phenyl-1,3,5-triazine, 2,2, 6, 6-tetrakis(2-cyanoethyl) cyclohexanon e, 1,1,1-tris(2-cyanoethyl)propanone-2 and 1,1,1-tris[2-(2,4-diamino-1,3,5- triazin-6yl)ethyl]propanone-2 have been complemented.