Novel Macromolecular and Biobased Flame Retardants Based on Cellulose Esters and Phosphorylated Sugar Alcohols.

The increasing demand to provide sustainably produced plastic materials requires, a.o., the development of biobased flame retardants (FRs) for applications where flame retardancy is essential. To meet those challenging new sustainability requirements, a set of novel phosphorus-containing cellulose esters were synthesized by an efficient two-step procedure. In the first step, cellulose was treated with acrylic anhydride to synthesize acrylate-functionalized cellulose esters-more specifically, cellulose acrylate butyrate (CeAcBu) and propionate (CeAcPr). Subsequently, phosphorylated anhydro erythritol (PAHE), synthesized from the sugar alcohol erythritol, was added to the acrylate-functionalized cellulose esters via Phospha-Michael addition. For comparison a cellulose ester based on 6H-Dibenzo[c,e][1,2]oxaphosphorin-6-on (DOPO) was prepared analogously. The acrylate-functionalized cellulose esters and novel FRs were characterized by NMR spectroscopy. TGA investigations of PAHE-functionalized CeAcBu revealed an onset temperature of decomposition (2% mass loss) of approx. 290 °C. The novel PAHE-based FR was incorporated into a polypropylene-polyethylene copolymer (PP-co-PE) together with poly-tert-butylphenol disulfide (PBDS) (8 wt.%/2 wt.%) as a synergist. The PP-PE samples achieved V2 classification in the UL 94 V test. In addition, specimens of a rapeseed oil-based polyamide containing PAHE-functionalized CeAcBu at 20 wt.% loading yielded a V2 rating with short burning times.

Phosphasilazanes as Inhibitors for Respirable Fiber Fragments Formed during Burning of Carbon-Fiber-Reinforced Epoxy Resins.

Carbon-fiber-reinforced polymer composites (CFRPs) exhibit additional hazards during and after burning due to respirable fragments of thermo-oxidatively decomposed carbon fibers. In this study, various phosphasilazanes are incorporated into the RTM 6 epoxy matrix of a CFRP to investigate their flame-retarding and fiber-protective properties via cone calorimetry. Residual carbon fibers are analyzed using SEM and EDX regarding their diameter and elemental composition of deposits. The decomposition process of phosphasilazanes is characterized by DIP-MS and infrared spectroscopy of char. Flame-retardant efficiency and mode of action are correlated with the chemical structure of the individual phosphasilazane and compared for neat resin and composite samples. Phosphasilazanes mainly acting in the condensed phase show beneficial fiber-protective and flame-retardant properties. Those with additional gas phase activity are less efficient. The phosphasilazanes degrade thermally via scission of the Si-N bond. The distribution and agglomeration of deposited particles, formed during the fire, influence the residual fiber diameters. Continuous layers show the best combination of flame retardancy and fiber protection, as observed for N-dimethylvinylsilyl-amidophosphorus diphenylester.

Mode of Action of Zn-DOPOx and Melamine Polyphosphate as Flame Retardants in Glass Fiber-Reinforced Polyamide 66.

In this study, the flame retardant effect of the Zn salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Zn-DOPOx), melamine polyphosphate (MPP) and their mixture was investigated towards the mode of action in glass fiber-reinforced polyamide 66 (PA 66 GF). The flammability was evaluated using UL 94 V and cone calorimetry. Influence on char formation was analyzed by SEM. Thermal decomposition of Zn-DOPOx and MPP was studied by TGA and ATR-FTIR. The release of gaseous PA 66 decomposition products was investigated using TGA-DTA-FTIR. Combining Zn-DOPOx and MPP leads to an improvement in flame retardancy, most pronounced for equal parts of weight. Mode of action changes significantly for Zn-DOPOx:MPP (1:1) compared to the sole components and a strong interaction between Zn-DOPOx and MPP is revealed, resulting in a more open char structure. Fuel dilution as well as less exothermic decomposition are essential for the mode of action of the combination. Through low HRR values and high CO/CO2 ratio during cone calorimetry measurements, a significant increase in gas phase activity was proven. Therefore, it is concluded that Zn-DOPOx:MPP (1:1) leads to a significant increase in flame retardancy through a combination of mode of actions in the gas and condensed phase resulting from the change in thermal stability.

Form-Stable Phase Change Materials Based on SEBS and Paraffin: Influence of Molecular Parameters of Styrene-b-(Ethylene-co-Butylene)-b-Styrene on Shape Stability and Retention Behavior.

In this work, the influence of molecular parameters of styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) triblock copolymer as matrix material in form-stable phase change material (FSPCM) on the thermo-mechanical properties and leakage behavior are studied. Various SEBS grades differing in their molecular weight, styrene content, and ethylene/butylene ratio are used as supporting matrix in composites with 90 wt.% paraffin. Thermo-mechanical properties are determined by rheological measurements. The results show phase transitions temperatures from solid to hard gel, hard gel to soft gel, and soft gel to gel fluid. Paraffin leakage in FSPCM is analyzed by mass loss over time in an oven at 60 °C. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are applied to determine the thermal energy storage capacity. Finally, the molecular weight and the styrene content are combined to the molecular weight of styrene block which is identified as the authoritative parameter for the thermo-mechanical properties of the SEBS/PCM composite.

Synthesis of Novel Polymeric Acrylate-Based Flame Retardants Containing Two Phosphorus Groups in Different Chemical Environments and Their Influence on the Flammability of Poly (Lactic Acid).

Novel polymeric acrylate-based flame retardants (FR 1-4) containing two phosphorus groups in different chemical environments were synthesized in three steps and characterized via nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mass spectrometry (MS). Polylactic acid (PLA) formulations with the synthesized compounds were investigated to evaluate the efficiency of these flame retardants and their mode of action by using TGA, UL94, and cone calorimetry. In order to compare the results a flame retardant polyester containing only one phosphorus group (ItaP) was also investigated in PLA regarding its flame inhibiting effect. Since the fire behavior depends not only on the mode of action of the flame retardants but also strongly on physical phenomena like melt dripping, the flame retardants were also incorporated into PLA with higher viscosity. In the UL94 vertical burning test setup, 10% of the novel flame retardants (FR 1-4) is sufficient to reach a V-0 rating in both PLA types, while a loading of 15% of ItaP is not enough to reach the same classification. Despite their different structure, TGA and cone calorimetry results confirmed a gas phase mechanism mainly responsible for the highly efficient flame retardancy for all compounds. Finally, cone calorimetry tests of the flame retardant PLA with two heat fluxes showed different flame inhibiting efficiencies for different fire scenarios.

Phosphorus-Containing Flame Retardants from Biobased Chemicals and Their Application in Polyesters and Epoxy Resins.

Phosphorus-containing flame retardants synthesized from renewable resources have had a lot of impact in recent years. This article outlines the synthesis, characterization and evaluation of these compounds in polyesters and epoxy resins. The different approaches used in producing biobased flame retardant polyesters and epoxy resins are reported. While for the polyesters biomass derived compounds usually are phosphorylated and melt blended with the polymer, biobased flame retardants for epoxy resins are directly incorporated into the polymer structure by a using a phosphorylated biobased monomer or curing agent. Evaluating the efficiency of the flame retardant composites is done by discussing results obtained from UL94 vertical burning, limiting oxygen index (LOI) and cone calorimetry tests. The review ends with an outlook on future development trends of biobased flame retardant systems for polyesters and epoxy resins.

EPR spectroscopic investigation of radical-induced degradation of partially fluorinated aromatic model compounds for fuel cell membranes.

EPR spectroscopic investigations of reactions between monomeric model compounds representing typical structural moieties of poly(aryl) ionomers and photochemically generated hydroxyl radicals are reported. Deoxygenated solutions of the model compounds (in a water/methanol mixture) containing hydrogen peroxide at defined pH values were exposed to UV light in the flow cell within the cavity of an EPR spectrometer. Spectra were analyzed by computer simulation and the formed radicals were assigned by comparing their g-factors and hyperfine coupling constants (hfccs) with those from the literature and from density functional theory (DFT) calculations. The relevance for polymer electrolyte membrane fuel cells (PEMFCs) and alkaline-anion exchange membrane fuel cells (AAEMFCs) is discussed.

La(1-x)Ba(1+x)GaO(4-x/2): a novel high temperature proton conductor.

In this communication we demonstrate high temperature proton conduction in the phase La(1-x)Ba(1+x)GaO(4-x/2), with conductivities significantly higher than reported for other phases containing tetrahedral ions, such as doped LaPO4.

Simple and sensitive method for the determination of celecoxib in human serum by high-performance liquid chromatography with fluorescence detection.

A simple method is described for the determination of the cyclooxygenase-2 specific inhibitor celecoxib in human serum by HPLC using the demethylated analogue as internal standard. After protein precipitation with acetonitrile, samples were extracted with chloroform. Separation was achieved on a Prontosil C18 AQ column (150x3 mm I.D., 3-microm particle size) at a flow-rate of 0.35 ml/min using water-acetonitrile (40:60, v/v) as the mobile phase. Using fluorescence detection with excitation at 240 nm and emission at 380 nm, the limit of quantification was 12.5 ng/ml for a sample size of 0.5 ml of serum. The assay was linear in the concentration range of 12.5-1500 ng/ml and showed good accuracy and reproducibility. At all concentrations intra- and inter-assay variabilities were below 11% with less than 9% error. The method was applied to the determination of celecoxib for pharmacokinetic studies in man.