Synthesis and flammability testing of epoxy functionalized phosphorous‐based flame retardants

Benin, Vladimir; Cui, Xuemei; Morgan, Alexander B.; Seiwert, Karl

doi:10.1002/app.42296

Cited by 18 publications

(20 citation statements)

References 30 publications

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“…• Although the synthesis of monomers 1 and 2 had been previously published, 11 this investigation resulted in a much better protocol, in terms of ease of isolation and purification, reproducibility of yields, and scale-up potential.…”

Section: Discussionmentioning

confidence: 99%

“…1 (dd, J 1 = 6.87 Hz, J 2 = 11.08 Hz, 2H), 5.26 (m, 2H), and 5.83 (m, 1H). 11,14 The allyl phosphonate 3 (15.83 g, 0.0832 mol) and sodium bicarbonate (23.75 g, 0.286 mol) were dissolved/suspended in 150 mL of acetone at 0-5°C. Separately, Oxone (49.60 g, 0.0807 mol) was dissolved in 120 mL of distilled water and added in portions to the reaction mixture to minimize foaming.…”

Section: 23mentioning

confidence: 99%

“…The preparation of PU samples followed a protocol that has been previously described 11 and is a modification of an earlier literature procedure. 19 Each Prep sample was generated by the use of 10 mol% of the corresponding oligomer as a comonomer.…”

Section: Polyurethane Sample Preparationmentioning

confidence: 99%

“…This study was based on the use of epoxyphosphonate 1 and epoxyphosphate 2 as the starting monomers. Both structures were recently reported, 11 but the preparation was considerably improved subsequently, particularly in terms of ability for scale up and ease of purification. New findings are therefore reported here in detail.…”

Section: Design and Execution Of Efficient Monomer Synthesismentioning

confidence: 99%

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New polyether diols as flame retardants for polyurethane: Derivatives of epoxy‐functionalized phosphonates and phosphates

et al. 2017

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SummaryPhosphorus-containing epoxides were used to generate several oligomeric polyether diols, which were in turn utilized in the preparation of model polyurethane (PU) samples, either as comonomers in the polymerization (Prep samples) or solvent blended into a priori prepared PU (Blend samples). The resultant samples were evaluated for heat release reduction potential using microcombustion calorimetry. Several variables were investigated in the oligomerization of the original epoxides, such as presence of initiator, epoxide comonomer, and solvent. The oligomer mixtures were thoroughly characterized, using NMR, mass spectrometry (MS), elemental analysis, and viscosity measurements. The final PU Prep samples were carefully analyzed to demonstrate and evaluate the degree of chemical incorporation of the polyether diols into the PU main chain.Results from the heat release studies demonstrated that incorporation of the phosphoruscontaining diol did lower flammability, but the structure of the original epoxide, as well as the oligoimerization conditions, had an effect on heat release reduction. The results are complex and require further study, but the phosphonate-based materials showed greater heat release reduction potential, both in the form of Prep and Blend samples, especially in one case of a Blend sample, where a notable amount of intumescent char was formed. KEYWORDS epoxides, flame retardancy, flammability testing, oligomers, phosphorus, polyurethanes 1 | INTRODUCTION Polyurethane (PU) foams, especially flexible foams, remain one of the largest fuel loads in the modern home. 1 These foams, should they ignite, can and will lead to catastrophic fire losses because of room flashover events. 2 While flame retardants are available for use today to lower the fire risk of PU foams, some of these flame retardants of small molecular size have been found to have environmental persistence issues, as well as negative bioaccumulation and toxicity profiles. 3 Further, the use of additives presents its own problem in that a small molecule flame retardant not chemically bound (through covalent bonds) to the PU matrix can slowly leach out over time, resulting in a loss of fire safety performance during the lifetime of the PU foam.There have been some attempts to address the additive issue by going to higher molecular weight/size molecules, such as oligomeric and polymeric flame retardants, which, should they migrate out of a polymer, present less of a bioaccumulation hazard. Still, what is mostly available for PUs today are small molecule flame retardant additives. The list of drawbacks of small molecule flame retardant additives leaves 3 other solutions (other than the use of sprinklers) that a fire protection engineer can use: barrier fabrics, conformal coatings, and reactive flame retardants.Barrier fabrics are currently being studied as a solution/replacement for flame retardant additives, but, these fabrics have their own drawbacks including fabrication issues, costs, and inability to protect against fire when the b...

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Section: Discussionmentioning

confidence: 99%

Section: 23mentioning

confidence: 99%

Section: Polyurethane Sample Preparationmentioning

confidence: 99%

Section: Design and Execution Of Efficient Monomer Synthesismentioning

confidence: 99%

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New polyether diols as flame retardants for polyurethane: Derivatives of epoxy‐functionalized phosphonates and phosphates

et al. 2017

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“…The syntheses and testing of potential reactive flame retardants for polyurethanes (PUs) have previously been reported by us. [8][9][10] New bis(phosphate)-containing molecules containing hydroxyl functionalities, as well as differing aliphatic/aromatic cores and semicarbazone substructures, are currently being studied and are the subject of this report. These compounds may exhibit enhanced heat release and flame retardancy effects, due to the presence of nitrogen in their structures.…”

Section: Introductionmentioning

confidence: 99%

Preparation and studies of new phosphorus‐containing diols as potential flame retardants

2017

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Summary Several new phosphorus‐containing potential flame retardants (FRs) were prepared and evaluated for heat release reduction potential, by incorporation of the molecules into polyurethane samples, generated from methylene diphenyl diisocyanate and 1,3‐propane diol. The potential FRs were all prepared from commercial diisocyanates, with the phosphorus‐containing substructure introduced as a semicarbazone. All of the target structures were diols, to facilitate their incorporation into a polyurethane main chain. The polyurethane samples were prepared via copolymerization, and analysis clearly demonstrated that the potential FRs were chemically incorporated, prior to heat release testing. The heat‐release reduction potential of these substances was evaluated using the microcombustion calorimeter. Results demonstrated that both heat release reduction potential and char formation were structure dependent. Some of the compounds containing an aromatic core had more effect on char formation (higher char yields) and peak heat‐release rate (lowered heat release) than just phosphorus content alone.

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The effects of aluminum and silicon phosphates on thermal stability and flammability of polystyrene

Chaparadza

Majoni

2022

J Chem Sci

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Synthesis and flammability testing of epoxy functionalized phosphorous‐based flame retardants

Cited by 18 publications

References 30 publications

New polyether diols as flame retardants for polyurethane: Derivatives of epoxy‐functionalized phosphonates and phosphates

New polyether diols as flame retardants for polyurethane: Derivatives of epoxy‐functionalized phosphonates and phosphates

Preparation and studies of new phosphorus‐containing diols as potential flame retardants

The effects of aluminum and silicon phosphates on thermal stability and flammability of polystyrene

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