Structure–Property Studies on a New Family of Halogen Free Flame Retardants Based on Sulfenamide and Related Structures

A wide variety of molecules containing S–N or S–N–S cores were synthesized, and their flame retardant properties in polypropylene (PP), low density polyethylene (LDPE) and polystyrene (PS) were investigated. In addition, polymers or oligomers bearing the sulfenamide functionality (SN) were also synthesized. It was shown that this radical generator family based on sulfenamides is very versatile in terms of structural modifications, and the thermal decomposition range can be easily adjusted by changing the R groups attached to the core. The thermal stabilities of the different sulfenamides were examined by thermogravimetric analysis (TGA). Radicals generated by the homolytic cleavage of the S–N or S–N–S bonds at an elevated temperature can effectively interact with the intermediate products of polymer thermolysis and provide excellent flame retardant properties. The choice of most suitable SN-structure varies depending on the polymer type. For polypropylene DIN 4102-1 B2 and UL94 VTM-2 classifications were achieved with only 0.5 to 1 wt % of sulfenamide, and, in some cases, no flaming dripping was observed. Also for LDPE thin films, sulfenamides offered the DIN 4102-1 B2 rating at low dosage. In the case of polystyrene, the very stringent UL94 V-0 classification was even achieved at a loading of 5 wt % of sulfenamide

Disulfides – Effective radical generators for flame retardancy of polypropylene

The potential of thirteen aliphatic, aromatic, thiuram and heterocyclic substituted organic disulfide derivatives of the general formula R-S-S-R’ as a new group of halogen-free flame retardants (FR) for polypropylene films have been investigated. According to DIN 4102-1 standard ignitibility test, for the first time it has been demonstrated that many of the disulfides alone can effectively provide flame retardancy and self-extinguishing properties to polypropylene (PP) films at already very low concentrations of 0.5 wt%. In an effort to elucidate the mechanism of the thermal decomposition of disulfide derivatives the fragmentation patterns of the evolved gases from a thermogravimetric analyzer (TGA) have been analyzed by simultaneous mass spectrometry (MS) and Fourier transform infrared spectrometry (FTIR). The main decomposition products initiated by homolytic scission of the S-S bond and/or scission of the C-S bond were identified as thiols, aliphatic and aromatic hydrocarbons, isothiocyanates (depending on the disulfide structures) with further evolution of elemental sulfur and sulfur dioxide at temperatures of above 300 oC and 450 oC, respectively. Based on this preliminary study, we have shown that disulfides represented by e.g. diphenyl disulfide (1), 5,5'-dithiobis(2-nitrobenzoic acid) (2), bis(1-phenyl-1H-tetrazol-5yl)-disulfide (4), 2-bisbenzothiazole-2,2′-disulfide (6) and N,N-dithiobis-(phtalimide) (10) constitute a new halogen-free family of additives for flame retarding of polypropylene

Triazene compounds as a novel and effective class of flame retardants for polyproplylene

Four triazene derivatives have been synthesized, i.e. bis-4,4'-(3,3'-dimethyltriazene)-diphenyl ether (1), bis-4,4'-(3,3'-diethyltriazene)-diphenyl ether (2), 2,2,6,6,-tetramethyl-1-phenylazo-piperidine (3) and 4-hydroxy-2,2,6,6-tetramethyl-1-phenylazopiperidine (4). Their thermal properties were determined by differential scanning calorimetry (DSC) and the fragmentation patterns were analysed by simultaneous mass spectrometry (MS) and Fourier transform infrared (FTIR) spectrometry of off-gases from a thermogravimetric analyser (TGA). The triazenes exhibited an exothermic decomposition peak at temperatures between 230 and 280 °C when the triazene units were homolytically cleaved into various aminyl, resonance-stabilized aryl radicals and different CH fragments with simultaneous evolution of elemental nitrogen. The potential of triazenes as a new class of flame retardants for polypropylene films was investigated by performing ignitability test in accordance to DIN 4102-1/B2 standard. Polypropylene samples containing very low concentration of only 0.5 wt% of any of these triazene (R-N1 = N2N3R'R") additives passed the test with B2 classification. Notably, no burning dripping could be detected. The average burning times are very short with exceptionally low weight losses. Based on this preliminary FR testing we have shown that the triazene compounds constitute a new and interesting family of radical generators for flame retarding of polymeric materials

Significance of Polymers with “Allyl” Functionality in Biomedicine: An Emerging Class of Functional Polymers

In recent years, polymer-based advanced drug delivery and tissue engineering have grown and expanded steadily. At present, most of the polymeric research has focused on improving existing polymers or developing new biomaterials with tunable properties. Polymers with free functional groups offer the diverse characteristics needed for optimal tissue regeneration and controlled drug delivery. Allyl-terminated polymers, characterized by the presence of a double bond, are a unique class of polymers. These polymers allow the insertion of a broad diversity of architectures and functionalities via different chemical reactions. In this review article, we shed light on various synthesis methodologies utilized for generating allyl-terminated polymers, macromonomers, and polymer precursors, as well as their post-synthesis modifications. In addition, the biomedical applications of these polymers reported in the literature, such as targeted and controlled drug delivery, improvement i aqueous solubility and stability of drugs, tissue engineering, and antimicrobial coatings, are summarized