Polymers from sulfamide. II. Evaluation and structure

Abstract

S P P kAcid-and tmse-catalyzed polymem involving sulfamide, melamine, and formaldehydeThe products are insoluble and their thermal have been prepared and investigated. stability does not exceed 225OC. in N2.The preparation of polymers by condensation of sulfamide, melamine, and formaldehyde was described in Part 1.l Samples of the more promising materials were synthesized for structure and evaluation purposes. The results of this investigation, as well as the results of additional studies on the related sulfamide-formaldehyde 1 :4 polymers, are discussed. (Here and throughout this paper 1:4, etc., indicates the molar ratio of reactants.) Data on solubility, thermal stability, infrared and x-ray structure analysis of these materials are included. EXPERIMENTALSome of the more promising compositions described in Part I' were selected for evaluation, and their preparations were also examined somewhat more closely than previously. PreparationsAcid-Catalyzed Sulfamide-Melamine-Formaldehyde 1 : 1 :4 (IA). (Prep aration 10, Table I, Part I.) A mixture of 6.0 g. (62.4 mmoles) of sulfamide, 7.8 g. (62.4 mmoles) of melamine, 20.4 g. of 37% aqueous formaldehyde solution [7.54 g. (249 mmoles) CH,O], and 4.5 ml. of O.558N hydrochloric acid (2.51 mmoles) was refluxed for 1 hr. at about 85" C. The pH of the resulting suspension was 2. Two phases remained throughout the course of the reaction. The product was a porous, tough, white solid, which was powdered and washed with 133 ml. of water, filtered, 489 490 FLORENTINE Er AI,.and then dried for 18 hr. a t 70°C. product obtained weighed 17.2 g. 100 ml. of water, filtered hot, and dried to constant weight, 15.3 g. a melting point of 27.5-280°C. (decomposes with red foaming).

Synthesis of Degradable Polysulfamides via Sulfur(VI) Fluoride Exchange Click Polymerization of AB-Type Monomers

“…While sulfamides are prevalent in pharmaceutical , or agrochemical molecules, very few polysulfamides have been synthesized thus far, which has prevented comprehensive studies of their properties including their hydrogen-bonding behavior. Polysulfamides were first accessed in the 1960s through condensation between aliphatic bis­(amine)­s and sulfamide (NH 2 SO 2 NH 2 ) at high temperatures that produced insoluble macromolecules that were not fully characterized. − In 2006, Rudkevich and co-workers synthesized an oligosulfamide ( M n ≈ 1.7 kg/mol) from a bis­(amine) monomer and a mixture of SO 2 gas, I 2 , and pyridine or triethylamine through the putative formation of unstable SO 2 I 2 species or derivatives . We hypothesized that the poor stability of the in situ generated SO 2 I 2 monomer hampered an efficient step-growth process, which led to low degrees of polymerization.…”

Investigating the Hydrogen Bond-Induced Self-Assembly of Polysulfamides Using Molecular Simulations and Experiments

“…Small molecules containing a sulfamide moiety − have gained a great amount of attention in medicinal chemistry, organocatalysis, − and molecular assembly. , By contrast, macromolecules with repeating sulfamide linkages (i.e., polysulfamides) have been seldomly synthesized, − preventing an in-depth exploration of their structure and properties. Michaudel and co-workers recently reported a general approach toward the synthesis of asymmetric sulfamides via sulfur­(VI)-fluoride exchange (SuFEx) click chemistry, which enables access to a wide range of polysulfamide structures via two polymerization processes. , The synthesized polysulfamides exhibit high thermal stability, tunable glass transition temperature ( T g ), and structure-dependent crystallinity.…”

Synthesis of unsymmetrical sulfamides and polysulfamides via SuFEx click chemistry

“…1a). [23][24][25] More recently, Rudkevich and coworkers synthesized oligomer 3b (M n ¼ 1.7 kg mol À1 ) using 1,4-phenylenediamine (1b) in combination with SO 2 , I 2 , and pyridine or triethylamine (Fig. 1a).…”