A Novel and Effective Synthetic Approach to 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) Derivatives

Artner, Johannes; Ciesielski, Michael; Ahlmann, Martin; Walter, Olaf; Döring, Manfred; Perez, Raul M.; Altstädt, Volker; Sandler, Jan K.W.; Schartel, Bernhard

doi:10.1080/10426500701407417

Cited by 43 publications

(30 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The second step was carried out via Michaelis–Arbuzov rearrangement using catalytic amounts of p ‐toluenesulfonic acid methylester at 180°C. The targeted phosphinate was isolated in good yields …”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Novel star‐shaped and hyperbranched phosphorus‐containing flame retardants in epoxy resins

Zhang

Wagner

Ciesielski

et al. 2011

Polymers for Advanced Techs

Self Cite

113

View full text Add to dashboard Cite

This report presents the synthesis and use of novel derivatives of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO, 1) and 5,5‐dimethyl‐1,3,2‐dioxaphosphorinan‐2‐one (DDPO, 2) as flame retardant additives for epoxy resins. DOPO‐based and DDPO‐based compounds were synthesized via nucleophilic substitution with 1,3,5‐tris‐(2‐hydroxyethyl) isocyanurate (THIC, 3) and subsequent oxidation (Schemes 1 and 2). Another trivalent DOPO derivative recently reported by our group was obtained by transamination followed by a Michaelis–Arbuzov rearrangement (Scheme 1). These products were blended into two epoxy resin systems [DEN 438 and diglycidyl ether of bisphenol A (DGEBA), both cured with dicyandiamide (DICY) and Fenuron] to obtain flame retardant thermosets. The flame retardancy and thermal properties of these epoxy resin systems were examined by UL 94‐V, Thermogravimetric analysis, and differential scanning calorimeter analysis. Furthermore, all reactions with phosphorus‐containing compounds were iterated employing the THIC oligomer, which was prepared via polycondensation of THIC (Scheme 3) using catalytic amounts of p‐toluenesulfonic acid. In addition, Atherton–Todd reaction with the THIC oligomer was studied as a novel synthetic method for phosphorus‐containing flame retardants (Scheme 4). The resulting products were utilized as flame retardants in epoxy resins and compared with the analogous monomeric compounds. Copyright © 2011 John Wiley & Sons, Ltd.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Synthesis of DOPO‐based and THIC‐based flame retardants 5 und 6 . Reaction conditions: a : triethylamine, chloroform, 0°C; b : 130°C, 2 mbar; c : tert ‐butyl hydroperoxide, toluene, 80°C; d : cat.…”

Section: Resultsmentioning

confidence: 99%

Novel star‐shaped and hyperbranched phosphorus‐containing flame retardants in epoxy resins

Zhang

Wagner

Ciesielski

et al. 2011

Polymers for Advanced Techs

Self Cite

113

View full text Add to dashboard Cite

show abstract

“…The conversion of DOPO into methyl‐DOPO is based on a patent of Dittrich et al 22 and an article of Artner et al 21 (Figure 1). Methyl‐DOPO was obtained with a yield of 97% (literature 95% 21) and characterized according to the melting point, 1 H‐, 13 C‐ and 31 P‐NMR, which were consistent with the literature.…”

Section: Methodsmentioning

confidence: 99%

“…The methyl ester of DOPO was found to show a very high flame retardancy efficiency for flex PU foams with low densities (22– 40 kg m −3 ) 19 which are known to be very difficult to protect against fire in its different applications 20. Some authors 21 explain the release of high concentrations of low molecular weight phosphorus‐containing species by a high ring tension of the phosphaphenanthrene structure of methyl‐DOPO. Quantum‐mechanical calculations revealed here a rather low ring tension which is not further discussed here.…”

Section: Introductionmentioning

confidence: 99%

Flame retardancy working mechanism of methyl‐DOPO and MPPP in flexible polyurethane foam

König

Kroke

2010

Fire and Materials

View full text Add to dashboard Cite

The chemical nature of flexible polyurethane (flex PU) foams, the low density, the high air permeability and the open cell structure cause this material to be highly flammable. The new phosphorus flame-retardant (FR) methyl-DOPO (9, 10-dihydro-9-oxa-methylphosphaphenanthrene-10-oxide) is known to show an excellent flame retarding behavior in flex PU foam by acting mainly in the gas phase. In this study, the FR working mechanism of methyl-DOPO and its ring-opened analogue MPPP (methylphenoxyphenyl-phosphinate) is investigated by TGA, TG-MS, FMVSS 302 and Cone Calorimeter measurements. Under TG-MS conditions comparable concentrations of low molecular weight species such as HPO, mathrmCH 3PO or PO 2 are released. These species are able to scavenge the H- and OH-radicals in the radical chain reactions of the flame leading to a significant increase in the CO/CO 2 ratio and the smoke density during cone calorimeter experiments. Finally, the flame retardancy of MPPP is determined to be less efficient in flex PU foam because of the higher vapor pressure compared with methyl-DOPO. Here, the vaporization of methyl-DOPO occurs in the same temperature region as the depolymerization of the urethane and the bisubstituted urea groups during pyrolysis of the foam leading to an optimal interaction

show abstract

“…In the literature there exists numerous reports dealing with the synthesis and flame retardant application of alkyl DOPO-derivatives [9][10][11]. Additionally, one can also find several reports dealing with the synthesis and application as flame retardant of alkoxy DOPO-derivatives [12]. In contrast to these derivatives one could find some publications dealing with amino DOPO-derivatives.…”

Section: Scheme 1 Dopo and Its Derivativesmentioning

confidence: 95%

Flame retardant polyurethanes based on novel phosphonamidate additives

Gaan¹,

Neisius²,

Cuchere³

et al. 2014

Fire Saf. Sci.

View full text Add to dashboard Cite

A Novel and Effective Synthetic Approach to 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) Derivatives

Cited by 43 publications

References 13 publications

Novel star‐shaped and hyperbranched phosphorus‐containing flame retardants in epoxy resins

Novel star‐shaped and hyperbranched phosphorus‐containing flame retardants in epoxy resins

Flame retardancy working mechanism of methyl‐DOPO and MPPP in flexible polyurethane foam

Flame retardant polyurethanes based on novel phosphonamidate additives

Contact Info

Product

Resources

About