Synthesis of DOPO-Based Phosphonamidates and their Thermal Properties

Neisius, N. Matthias; Lutz, Maximilian; Rentsch, Daniel; Hemberger, Patrick; Gaan, Sabyasachi

doi:10.1021/ie403677k

Cited by 118 publications

(90 citation statements)

References 39 publications

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“…The three novel compounds were designed in order to possess improved flame retardation potential, but also for a wide range of applications based on their higher melting points and increased stability, which are prerequisites for their use in the production of plastic materials (Buczko et al 2014; Gaan et al 2013, 2015; Neisius et al 2014; Salmeia and Gaan 2015; Salmeia et al 2015; Qiang et al 2011). In contrast to the current practice of investigating the potential harmful properties of flame retardants after their introduction into the market, we applied here a series of human in vitro screening assays to allow a fundamental toxicological classification before the production and application of halogen-free bis -DOPO compounds on an industrial scale.…”

Section: Discussionmentioning

confidence: 99%

“…In order to improve its flame retardation potential and influence its physico-chemical parameters, such as its melting point, to allow industrial application in different plastic materials, novel phosphonamidate and phosphonate and phosphinate derivatives of DOPO have been developed (Gaan et al 2009, 2013, 2015; Buczko et al 2014; Neisius et al 2014; Salmeia and Gaan 2015; Salmeia et al 2015), but have not been evaluated with respect to their toxicological potential. In the combustion process, phosphonamidate DOPO derivatives primarily act in the vapor phase by forming phosphorus-containing radical species (PO · ) (Salmeia and Gaan 2015; Salmeia et al 2015), which interact with · OH or H · radicals (Eq.…”

Section: Introductionmentioning

confidence: 99%

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Multiparameter toxicity assessment of novel DOPO-derived organophosphorus flame retardants

Hirsch

Striegl²,

Mathes

et al. 2016

Arch Toxicol

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Halogen-free organophosphorus flame retardants are considered as replacements for the phased-out class of polybrominated diphenyl ethers (PBDEs). However, toxicological information on new flame retardants is still limited. Based on their excellent flame retardation potential, we have selected three novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives and assessed their toxicological profile using a battery of in vitro test systems in order to provide toxicological information before their large-scale production and use. PBDE-99, applied as a reference compound, exhibited distinct neuro-selective cytotoxicity at concentrations ≥10 µM. 6-(2-((6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)amino)ethoxy)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide (ETA-DOPO) and 6,6′-(ethane-1,2-diylbis(oxy))bis(6H-dibenzo[c,e][1,2]oxaphosphinine-6-oxide) (EG-DOPO) displayed adverse effects at concentrations >10 µM in test systems reflecting the properties of human central and peripheral nervous system neurons, as well as in a set of non-neuronal cell types. DOPO and its derivative 6,6′-(ethane-1,2-diylbis(azanediyl))bis(6H-dibenzo[c,e][1,2]oxaphosphinine-6-oxide) (EDA-DOPO) were neither neurotoxic, nor did they exhibit an influence on neural crest cell migration, or on the integrity of human skin equivalents. The two compounds furthermore displayed no inflammatory activation potential, nor did they affect algae growth or daphnia viability at concentrations ≤400 µM. Based on the superior flame retardation properties, biophysical features suited for use in polyurethane foams, and low cytotoxicity of EDA-DOPO, our results suggest that it is a candidate for the replacement of currently applied flame retardants.Electronic supplementary materialThe online version of this article (doi:10.1007/s00204-016-1680-4) contains supplementary material, which is available to authorized users.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Multiparameter toxicity assessment of novel DOPO-derived organophosphorus flame retardants

Hirsch

Striegl²,

Mathes

et al. 2016

Arch Toxicol

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“…The new broad peak around 1032 cm -1 and a much higher peak at 889 cm -1 from EP-2.5 at 380 °C suggest the release of compounds containing phosphorus, 31 which may act in gas-phase flame inhibition. 33,34 In addition, the peak intensity of pyrolytic products from EP-2.5 is much larger than that from EP-0 at 380 °C, especially for hydrocarbons and aromatic compounds. However, the intensity of peaks of C=O (1766 cm -1 ), CO 2 (2383 and 2302 cm -1 ) and CO (2180 and 2108 cm -1 ) from EP-2.5 is smaller than that from EP-0 at 380 and 400 °C, indicating that the degradation process of epoxy resin matrix is changed by incorporation of DPPA.…”

Section: Tga-ftir Analysismentioning

confidence: 97%

Intumescent flame retardancy of a DGEBA epoxy resin based on 5,10-dihydro-phenophosphazine-10-oxide

et al. 2015

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5,10-Dihydro-phenophosphazine-10-oxide(DPPA) served as a co-curing agent of 4, 4'-diaminodiphenylmethane for the curing reaction of bisphenol A diglycidyl ether (DGEBA) epoxy resin (EP). 1 H NHR spectrum tracking the reaction process of DPPA with DGEBA revealed that P-H bond of DPPA had the higher reactivity than its N-H bond for reacting with epoxy group. DPPA could promote the curing reaction of DDM with DGEBA. DPPA endowed epoxy resin with high flameretardant efficiency due to the unique combination of phosphorus and nitrogen in the phenophosphazine ring. The cured epoxy resin could pass V-0 rating of UL-94 test with limiting oxgen index (LOI) of 33.6% at only 2.5 wt% DPPA. The reduced peak heat release rate and total heat release, and increased char yield further verified the excellent flame retardancy for EP. Flame-retardant mechanism of the epoxy resin was investigated by thermogravimetry-fourier transform infrared spectrometry (TG-FTIR), scanning electron microscopy, element analysis and FTIR spectrometry. The results indicated that DPPA catalyzed epoxy resin matrix to form the rigid intumescent char and to generate the blowing-out effect.

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“…28 However, regardless of the easy handling of this reaction, it has found no commercial successes as CCl 4 is a carcinogen and depletes the ozone. In these cases, P(O)─H bond has been transformed to P─Cl via the use of several chlorinating agents such as tert-butyl hypochlorite (t-BuOCl), 31 chlorine gas (Cl 2 ), 32-34 copper(II) chloride (CuCl 2 ), 35 sulfuryl chloride (SO 2 Cl 2 ), 36 n-chlorosuccinimide (NCS), 22,37 and trichloroisocyanuric acid (TCCA). In these cases, P(O)─H bond has been transformed to P─Cl via the use of several chlorinating agents such as tert-butyl hypochlorite (t-BuOCl), 31 chlorine gas (Cl 2 ), 32-34 copper(II) chloride (CuCl 2 ), 35 sulfuryl chloride (SO 2 Cl 2 ), 36 n-chlorosuccinimide (NCS), 22,37 and trichloroisocyanuric acid (TCCA).…”

Section: General Synthesis Methodsmentioning

confidence: 99%

Recent developments in P(O/S)–N containing flame retardants

Nazir

Gaan

2019

J of Applied Polymer Sci

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Synthesis of organophosphorus compounds containing nitrogen as heteroatom and its application as a flame retardant (FR) have attracted much attention in the academic and industrial communities over the past decade. Such compounds are relatively easy to synthesize and offer advantages such as high thermal stability, which is useful for high temperature processing, improved char stability, density, and yield during the thermal decomposition of polymer, and release phosphorus species active in the flame inhibition process. Though a variety of phosphorus-nitrogen (P-N) compounds can be found in the literature, this review mostly summarizes the recent (since 2013) development in phosphorus (O)-nitrogen containing flame retardants which have been published in peer-reviewed journals. General strategies of synthesizing P(O)-N compounds as FRs from various phosphorus-based starting materials are highlighted in this review. Some of the most common classes of researched P(O)-N containing compounds as FRs include the phosphinamides, phosphonamides, phosphoramides, phosphoramidates, phosphorodiamidates, phosphonamidates and their thio counterparts which are usually obtained via a one-or two-step synthetic strategy. Incorporation of these compounds as FRs in various polymer systems such as polyurethane, epoxy resins, polyamides, cellulose, polylactide, poly(butylene terephthalate), polycarbonates, and acrylonitrile-butadiene-styrene are discussed in detail in this review. Special emphasis on the various fire and thermal performances of the new materials are also summarized. The mechanical performance of new materials and the influence of these additives on polymer processing are also briefly discussed.

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Synthesis of DOPO-Based Phosphonamidates and their Thermal Properties

Cited by 118 publications

References 39 publications

Multiparameter toxicity assessment of novel DOPO-derived organophosphorus flame retardants

Multiparameter toxicity assessment of novel DOPO-derived organophosphorus flame retardants

Intumescent flame retardancy of a DGEBA epoxy resin based on 5,10-dihydro-phenophosphazine-10-oxide

Recent developments in P(O/S)–N containing flame retardants

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