Sulfur-based copolymeric polyamidoamines as efficient flame-retardants for cotton

The polyamidoamine derived from N,N'-methylenebisacrylamide (M) and glycine (G), M-G, has been shown to be an effective flame-retardant (FR) for cotton in horizontal flame spread tests (HFST), extinguishing the flame at 5% add-on. Its activity was attributed to its intrinsic intumescence. In vertical flame spread tests (VFST), M-G failed to extinguish the flame even at 30% add-on. Conversely, in VFST, the polyamidoamine derived from M and cystine (C), M-C, inhibited cotton combustion at 16% add-on, but in HFST failed to extinguish the flame below 12% add-on. Its activity was ascribed to the release of sulfur-containing volatiles acting as radical scavengers. In this work, the FR effectiveness of M-Gm-Cn copolymers with different G/C ratio was compared with that of the M-G and M-C homopolymers and of M-G/M-C blends of the same compositions. In HFST, both copolymers and blends extinguished the flame. In particular, M-G50-C50 and (M-G/M-C)50/50 extinguished the flame, even at 7% add-on. In VFST, the copolymers with 6550% M-C units, similar to M-C, inhibited cotton combustion at 16% add-on. At the same add-on, the M-G/M-C blends failed to extinguish the flame. It may be concluded that, in contrast to blends, copolymers combined the merits of both homopolymers in all tests

Polyamidoamines derived from natural α-amino acids as effective flame retardants for cotton

In this paper, bioinspired polyamidoamines (PAAs) were synthesized from N,N′-methylene bisacrylamide and nine natural α-amino acids: L-alanine, L-valine, L-leucine (M-LEU), L-histidine, L-serine, L-asparagine, L-glutamine (M-GLN), L-aspartic acid and L-glutamic acid (M-GLU) and their performance as flame retardants (FRs) for cotton were determined. The aim was to ascertain if the ability to protect cotton from fire by the process of intumescing, previously found for the glycine-derived M-GLY, was a general feature of α-amino acid-derived PAAs. None of the PAAs ignited by flame impingement, apart from M-LEU, which burned for a few seconds leaving 93% of residue. All of them formed carbon-and oxygen-rich, porous chars with a graphitic structure in the air at 350◦C, as revealed by X-ray photoelectron spectroscopy. All samples were tested as FRs for cotton by horizontal flame spread tests. At a 5% add-on, M-GLU and M-GLN extinguished the flame. The same results were obtained with all the other PAAs at a 7% add-on. The α-amino acid residues influenced the FR performance. The most effective were those that, by heating, were most suitable for producing thermally stable cyclic aromatic structures. All PAA-treated cotton samples, even when burning, left significant residues, which, according to scanning electron microscopy analysis, maintained the original cotton texture

Linear Polyamidoamines as Novel Biocompatible Intumescent Flame Retardants for Cotton

Since the middle of the last century, many industrial and academic researchers have devoted a lot of effort to the development of safe and effective flame- retardants (FR). As regards cotton, phosphorylated compounds were the predominant FR for several decades [1] despite many of them had been shown to be bioaccumulative.[1] Recently, biomolecules including proteins have been proposed as FR.[2] Many linear polyamidoamines (PAAs), a family of synthetic polymers with exceptional structural versatility,[3] have high thermal stability coupled with chain structure and side substituents reminding those of proteins.[4] These features suggested that PAAs could act as FR. This presentation reports on the results obtained with a library of eight PAAs applied as coatings on cotton fabrics from aqueous solutions. All tested PAAs warrant remarkable potential as surface-confined intumescent FR. In ignitability tests, six of them exposed to direct flame for 10 s do not burn, but produce carbonaceous crusts sheltering the underneath sample. Thermogravimetric analyses show that at T 65 400 \ub0C all PAAs leave in air substantial char residues that oxidize at T > 500 \ub0C. At 450 \ub0C they form porous carbonaceous structures indicating the tendency to intumesce. In horizontal flame spread tests, cotton stripes impregnated with most PAAs extinguish flame at add-ons ranging from 4 to 20%, whereas untreated cotton vigorously burns without leaving residues. Upon 35 kW/m2 heat flux, all PAA-treated samples significantly reduce the main combustion parameters. References [1] R. A. Horrocks, Polym. Degrad. Stab. 2011, 96, 377. [2] L. Costes, F. Laoutid, S. Brohez, P. Dubois, Mater. Sci. Eng. Report, R. 2017, 117, 1. [3] P. Ferruti, J. Polym. Sci, Part A: Polym. Chem. 2013, 51, 2319. [4] F. Danusso, P. Ferruti, Polymer 1970, 11, 88

Highlight on the Mechanism of Linear Polyamidoamine Degradation in Water

This paper aims at elucidating the degradation mechanism of linear polyamidoamines (PAAs) in water. PAAs are synthesized by the aza-Michael polyaddition of prim-monoamines or bis-sec-amines with bisacrylamides. Many PAAs are water-soluble and warrant potential for biotechnological applications and as flame-retardants. PAAs have long been known to degrade in water at pH 65 7, but their degradation mechanism was never explored in detail. Filling this gap was necessary to assess the suitability of PAAs for the above applications. To this aim, a small library of nine PAAs was expressly synthesized and their degradation mechanism in aqueous solution studied by 1H-NMR in different conditions of pH and temperature. The main degradation mechanism was in all cases the retro-aza-Michael reaction triggered by dilution but, in some cases, hints were detected of concurrent hydrolytic degradation. Most PAAs were stable at pH 4.0; all degraded at pH 7.0 and 9.0. Initially, the degradation rate was faster at pH 9.0 than at pH 7.0, but the percent degradation after 97 days was mostly lower. In most cases, at pH 7.0 the degradation followed first order kinetics. The degradation rates mainly depended on the basicity of the amine monomers. More basic amines acted as better leaving groups

Flame retardant multilayered coatings on acrylic fabrics prepared by one-step deposition of chitosan/montmorillonite complexes

Multilayered coatings deposited using the layer-by-layer (LbL) assembly technique have attracted great interest in recent years as a sustainable and efficient solution for conferring flame retardant properties to fabrics. The unique structure and interaction established upon the coating assembly are the key factors for successful flame retardant properties. In this study we aimed at the deposition of multilayered coatings comprising chitosan and montmorillonite with a LbL-like structure and interactions by the simple processing of compacted chitosan/montmorillonite complexes obtained by the direct mixing of an oppositely charged solution/suspension. Upon drying, the prepared complex yielded a continuous coating characterized by a brick-and-mortar multi-layered structure, in which oriented clay nanoplatelets were held together by a continuous chitosan matrix. When deposited on acrylic fabrics these coatings were able to suppress the melt-dripping phenomenon, and at 10 and 20% add-ons achieved self-extinguishing behavior within a few seconds after ignition. Cone calorimetry testing revealed an increase in time to ignition (up to +46%) and considerable reductions of the rates at which heat is released (up to -62 and -49% for peak of heat release rate and total heat release, respectively). A reduction in the total smoke release (up to -49%) was also observed

Poly(ethylene terephthalate)-carbon nanofiber nano composite for fiber spinning; properties and combustion behavior

Carbon nanofiber (CNF)-polyethylene terephthalate (PET) blends were previously prepared by melt blending and, subsequently, melt spun in order to obtain nanostructured fibers characterized by high flame retardant properties and resistance to the combustion. The morphological analysis showed that CNFs are homogeneously distributed and finely dispersed within PET matrix. The mechanical properties in tensile testing of the fibers change in the presence of CNFs: the elongation at break increases, whereas the tenacity and the tensile strength decrease. The combustion tests by cone calorimetry reveal a relevant decrease of heat release rate, total heat evolved and total smokes released by the nanocomposites as compared to neat PET

Nonlinear models of the bump cepheid HV 905 and the distance modulus to the large magellanic cloud

Nonlinear pulsation models have been used to simulate the light curve of the LMC bump Cepheid HV 905. In order to reproduce the light curve accurately, tight constraints on the input parameters M, L, and T-eff are required. The results, combined with accurate existing V and I photometry, yield an LMC distance modulus of 18.51 +/- 0.05, and they show that the luminosity of HV 905 is much higher than expected from the mass-luminosity relation of stellar evolution theory. If we assume that the pulsation models are accurate, this suggests that there is a larger amount of convective core overshoot during the main-sequence evolution of stars with M similar to 5 M. than is usually assumed