The Pharma Innovation Journal 2018; 7(5): 380-386

ISSN (E): 2277- 7695

ISSN (P): 2349-8242
NAAS Rating: 5.03 A review of non-halogenated flame retardant
TPI 2018; 7(5): 380-386
© 2018 TPI
www.thepharmajournal.com
Received: 07-03-2018
Sanjay D Jadhav
Accepted: 09-04-2018
Abstract
Sanjay D Jadhav Recent patent and literature indicate a growing interest in non-halogenated flame retardants are on the
Research Scholar Chemistry, fast growing track due to the environmental consideration, although sometimes efficiency, lower density
Shri. Jagdishprasad Jhabarmal & good light stability are the significant factors. Patent published on the flame retardancy of
Tibrewala University, polycarbonate & its blends significantly exceed the number of patent on the flame retardancy of any
Vidyanagari, Jhunjhunu,
other polymer. Bridged aromatic phosphates have found broad applications because of there good
Rajasthan, India
thermal stability, high efficiency & low volatility.
Flame retardant has very important role to play in today’s science and technological field and considering
the importance various researcher have studied various aspect and application areas for the same.
Similarly various innovative molecules have been invented and tried various researchers but this is not
the end of the research.
This review summarizes main advances published over the period of last 20 years, outlining the work
carried out on synthesis of non-halogenated flame retardant compounds and application of it. Another
actively reported group of compounds are the metal salt of phosphorous compounds which have been
found to be particularly effective in poly butylene terepthalate & polycarbonate. These products are
synergistic with a number of phosphorous & nitrogen containing compounds which seems to be a very
efficient and commercially useful in nylon

Keywords: Flame retardant, reduction, Organohalogens, Organophosphorus, reactive, additive,

synergism, polycarbonates and polyurethanes

1. Introduction
Halogen containing flame retardant particularly based on bromine have played & continue to
play a large part in flame retardancy. However, mainly because of environmental concern &
end of life issue, there has been a growing interest in non-halogenated solutions. The large
number of the patent and non-patent literature is focused on non-halogenated flame retardants.
In this review, the more recent developments in non-halogenated flame retardants for several
major group of plastic, epoxy & commercial development.
Flame retardants find an important place in the list of various additives that imparts special
characters to the plastics and other consumer products to meet flammability standards for
furniture, textiles, electronics, and insulation. Typically Flame retardants are chemicals used in
thermoplastics, thermo sets, textiles and coatings that inhibit or resist the spread of fire.
The question of whether the halogen need replacing is still open question that is not entirely
resolved on scientific background [1, 2]. Some halogen containing like tris (dibromo propyl)
phosphate was banned in the late 1970.Pentabromodiphenyl ether, tetrabromo bisphenol a are
recently banned in Europe & US. However all user of flame retardants want to have an
alternative either to offer on the market. Thus research on halogen alternative such as
phosphorous & nitrogen based is very alternative to the bromine are finding market acceptance
[3]
.

2. Main class of flame retardants

These chemicals can be separated into several different classes are listed below
 Halogen based Flame retardant: This class includes organ chlorines such as chlorendic
acid derivatives and chlorinated paraffin; organobromines such as decabromodiphenyl
Correspondence
ether (decaBDE), decabromodiphenyl ethane (a replacement for deca BDE).
Sanjay D Jadhav Organo-halogen chemicals (including all BFRs) to be banned globally. The challenges of
Research Scholar Chemistry, finding substitutes for banned halogen-containing flame retardants include:
Shri. Jagdishprasad Jhabarmal Lower flame retardancy: Only 10 wt% of BFRs is equivalent to about 30-50% by wt of
Tibrewala University, inorganic FRs.
Vidyanagari, Jhunjhunu,
Rajasthan, India
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High cost: Inorganic FRs is low-cost but require high polyesters, phenolics, epoxies and coatings for textiles.
loading. New HFFRs, on the other hand, are mostly  In organic flame retardants: The most common
costlier. The cost ratios (£) of BF-FR with phosphorous inorganic flame retardants are the hydroxides or
based and nonphosphorous based HFFR are about 1:6 aluminium and magnesium, huntite and Hydromagnesite
and 1:2 respectively. [8, 9, 10, 11, 12]
. Aluminium trihydroxide (ATH) is by far the
Higher thermal stability: Many HFFRs decompose at most widely used flame retardant. It is very inexpensive,
higher temperature (about 400 °C) than their halogenated but usually requires higher loadings in polymers of up to
counterparts (about 3300C). more than 65%. Its mode of action is based on the release
Melt-dripping: Melt dripping occurs with most polymers of water (Endothermic process) which cools the polymer
e.g. polyethylene, polypropylene, PET, ABS and so on. and dilutes the flame zone. Magnesium hydroxide
Flammable drips act as secondary ignition sources. FRs (MDH) is used in polymers which have higher processing
should make drips non-flammable. temperatures, because it is stable up to temperatures of
Deterioration in Mechanical Properties: The deterioration around 310 °C versus ATH which decomposes around
of mechanical properties increase proportionately with 210 °C.
the amount of FR. Therefore, the deterioration is more Aluminum hydroxide flame retardants (white powder) for
with less efficient FRs [4] processing temperatures up to about 210 °C, for wire and
 Organophosphorus compounds: This class includes cable, electronic and electrical components based on
organophosphates such as triphenyl phosphate (TPP), thermosets resins, building materials, mass
resorcinol bis (diphenylphosphate) (RDP), Bisphenol A transportation, paints and varnishes, paper and plaster
diphenyl phosphate (BADP), and tricresyl phosphate with organic binder.
(TCP); phosphonates such as dimethyl methyl Magnesium hydroxide flame retardants (white powder)
phosphonate (DMMP) and phosphinates such as for processing temperatures up to about 310 °C for wire
aluminum diethyl phosphonate [5, 6]. and cable, electronic and electrical components based on
Phosphorus-containing flame retardants cover a wide polyamide resins, building materials.
range of inorganic and organic compounds and include There are other minerals that show flame retarding effects
both reactive products which are chemically bound into and are used in commercial applications. Most of them
the polymer material as well as additive products which are used as synergists i.e. they enhance the performance
are integrated into the material by physical mixing only of other flame retardants or they are used for specific
[7]
. They have a broad range of applications, and a good effects like the suppression of smoke formation,
fire safety performance. The most important phosphorus- increasing char formation etc. For example, borates are
containing flame retardants are phosphate esters, used as mixtures of boric acids and borax as flame
phosphonates and phosphinate. retardants for cellulose (cotton) and of zinc borate for
Phosphorus-containing flame retardants are widely used PVC and other plastics like polyolefins, Elastomer,
in standard and engineering plastics, polyurethane foams, polyamides, or epoxy resins. In halogen-containing
thermosets, coatings, and textiles. Phosphate esters are systems, zinc borate is used in conjunction with antimony
mainly used as flame retardant plasticizers in oxide (mainly to reduce cost), while in halogen-free
polyvinylchloride (PVC, alkyl/aryl phosphates) and systems it is normally used in conjunction with ATH,
engineering plastics, particularly in polyphenylene MDH or red phosphorus. In some particular applications
oxide/high impact polystyrene (PPO/HIPS), zinc borate can be used alone. Boron containing
polycarbonate/ acrylonitrile butadiene styrene (PC/ABS) compounds act by stepwise release of water and
blends and polycarbonate (PC, e.g. triphenylphosphate, formation of a glassy coating which protects the surface.
resocinol-and bisphenol A-bis-(diphenyl) phosphate). Zinc compounds were initially developed as smoke
The latter are widely used in IT housings requiring high suppressants for PVC (Zinc hydroxystannate). Later it
fire safety levels. Other applications include phenolic was found that they also act as flame retardants in certain
resins and coatings. Phosphates, phosphonates and plastics mainly by promoting char formation.
phosphinates are used as reactive phosphorus containing Other inorganic fillers like talcum or chalk (calcium
flame retardants in flexible polyurethane foams for carbonate) are sometimes called flame retardants, their
automotive and building applications. Additive organic mode of action is simply by dilution, i.e. they they reduce
phosphinates are a new class of flame retardants for use the amount of polymer and hence the fire load.
in engineering plastics, particularly in polyamides.  Nitrogen based Flame Retardants
Specific reactive phosphorus flame retardants are used in Nitrogen compounds are a small but rapidly growing
polyester fibres and for wash resistant flame retardant group of flame retardants (FR) which are in the focus of
textile finishes. Other reactive organophosphorus public interest concerning environmentally friendly flame
compounds can be used in epoxy resins in printed circuit retardants. Today their main applications are melamine
boards. for polyurethane flexible foams, melamine cyanurate in
Flame retardant grades based on red phosphorus are nylons, melamine phosphates in polyolefins, melamine
mainly used in glass fibre reinforced polyamide 6 and 66. and melamine phosphates or dicyandiamide in
Further applications are in polyethylene and ethylene intumescent paints, guanidine phosphates for textiles and
vinyl acetate (EVA), polyurethane foam, and guanidine sulfamate for wallpapers. Their main common
thermosettings resins (unsaturated polyesters and advantages are their low toxicity, their solid state and, in
epoxies). Ammonium polyphosphate grades are primarily case of fire, the absence of dioxin and halogen acids as
used in intumescent coatings. They are also found in rigid well as their low evolution of smoke. Their efficiency lies
and flexible polyurethane foams and polyolefins between that of halogen compounds and that of
(injection moulded), in formulations for unsaturated aluminum trihydrate and magnesium hydroxide. The
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metallic hydroxides split off water and are 2-yl) amino]-3,9-dioxido-2,4,8,10-tetraoxa-3,9-

environmentally friendly, but their low activity requires diphosphaspiro [5.5] undecan-3-yl}oxy) ethyl
high concentrations which change the mechanical methacrylate (EADP), synthesized from phosphorus
properties of the matrix that they are applied to. In oxychloride, pentaerythritol, hydroxyethyl methacrylate,
contrast to many halogen compounds, flame retardants and melamine. EADP (Figure 2) exhibited excellent
based on nitrogen do not interfere with the set of thermal stability and char-forming ability without
stabilizers added to every plastic material. Recyclability affecting tensile strength of polypropylene [15].
has become important as many plastics are recycled. Rigid polyurethane foam (RPUF) is very flammable and
Flame retarded materials based on nitrogen compounds releases toxic gases while burning. Traditional IFRs are
are suitable for recycling as the nitrogen flame retardants mixtures, and are not compatible with the RPUF matrix
[16]
have high decomposition temperatures. In the field of . A phosphorousnitrogen (P-N) containing IFR,
cable jacketing they evolve less corrosive gases during toluidine spirocyclic pentaerythritol bisphosphonate
combustion and do not damage the electrical (TSPB), (Figure 3) exhibited better compatibility with
installations. Flame retardants based on nitrogen are RPUF and lesser negative influence on the mechanical
environmentally friendly because they do not add any properties of TSPB-RPUF forming compact and smooth
new element to those already present in the polymers char [17]. Waterborne polyurethane (WPU) has good
such as polyurethanes, nylons and ABS. In regard to applicability including fabric coating as against
waste disposal they are comparable with fertilizers as conventional solvent borne polyurethanes. Octahydro-2,
they possess the same elements of importance, namely 7-di (N, N-dimethylamino)-1, 6, 3, 8, 2, 7-
nitrogen and phosphorous. In comparison with metallic dioxadiazadiphosphecine (ODDP) (Figure 4), with bi-
hydroxides they are more efficient and deteriorate the phosphonyl in a cyclic compound, was synthesized.
mechanical ODDP reacted phosphorus-nitrogen synergistic HFFR
 Silicon based flame retardants: Silicon-based materials waterborne PU (DPWPU) has excellent flame retardancy
are potential flame retardants as they produce protective due to the presence of ODDP. The LOI value of DPWPU
surface coatings during a fire, caused by a low rate of is 30.6% with UL-94, V-0 classification obtained at 15 wt
heat released. Low levels of silicone in certain organic % ODDP [18].
polymer systems have been reported to improve their  Nanocomposites: Nanocomposites is a multiphase solid
LOI and UL-94 performance. Some compounded silicone material where one of the phases has one, two or three
(polydimethylsiloxane-type) contains dry powders with a dimensions of less than 100 nanometres, or structures
variety of organic plastics. Particularly in PS, they having nanoscale repeat distances between the different
showed that an additive level, as low as 1 to 3%, reduces phases that make up the material. Polymer layered-
the rate of heat released by 30 to 50%. They reported silicate nanocomposites (PLSNs) with silicate enhance
similar improvements in HIPS, PP, PS-blends EVA. mechanical properties, increase heat-distortion
These compounds can either be physically mixed with temperatures, improve thermal stability, decrease
the base material (additive flame retardants) or gas/vapour permeability and reduce flammability [19]. The
chemically bonded to it (reactive flame use of P–N flame-retardant with montmorillonite (MMT)
retardants).Despite restrictions on further production in as a flame-retardant synergist for flame-resistant
some countries, consumer products previously treated thermoplastics such as PP, PA6, and PA66 has been
with banned retardants are still in use and continue to reported [20]. Chemically, montmorillonite is hydrated
release toxic chemicals into the environment, and the sodium calcium aluminium magnesium silicate hydroxide
worldwide use of organohalogens retardants continues to (Na, Ca) 0.33 (Al, Mg) 2 (Si4O10) (OH) 2 •nH2O.
increase [13]. Montmorillonites swell or expand considerably more
 Intumescent Flame retardants: Intumescences is the than other clays due to water penetrating the interlayer
result of a combination of charring and foaming at the molecular spaces and concomitant adsorption. By
surface of the burning polymer, which protects the exchanging sodium cations for organic cations the
underlying material from the action of the heat or flame. surface energy of MMT decreases and the interlayer
Intumescent FRs (IFRs) is often used for applications spacing expands. The resulting material is called
requiring high levels of flame retardancy. They are highly organoclay [21]. Thermoplastic poly (ester ether)
efficient and low toxic. They provide very robust fire elastomers (TPEEs) are easily ignited and rapidly burned.
safety and flame resistance performance. The carbon TPEE nanocomposites with phosphorus-nitrogen (P-N)
agent forms multicellular charred layers, the char may be flame retardants and organic montmorillonite (o-MMT)
soft or hard [14]. Soft char IFRs: composed of a carbon were prepared by melt blending. A significant fire-
source pentaerythritol (PER), acid source (ammonium retardant effect was induced in TPEE and rendered a V-0
polyphosphate) and a gas-blowing additive (melamine) classification in the UL 94 test [22]. Organically treated
harder char IFRs: composed of sodium silicates and layered silicates (clays), carbon nano-tubes/nano-fibres,
graphite. These are suitable for use in plastic pipe or other submicron particles at low loading (1-10 wt%)
firestops as well as exterior steel fireproofing. PER is are used for polymer nanocomposites. The polymer
quite costly. A possible substitute is green carbon agent is nanocomposites greatly lower the base flammability of a
chitosan (CS), obtained by the alkaline deacetylation of material. Recent research has suggested that combining
abundantly naturally occurring chitin. A good synergistic nanoparticles with traditional fire retardants (e.g.
effect observed when chitosan/urea compound based intumescent) or with surface treatment (e.g. plasma
phosphonic acid melamine salt (HUMCS), was added to treatment) effectively decreases flammability [23]. When
an IFR system for polypropylene (PP) [14]. A reactive, polymer nanocomposite is used, very little additive is
intumescent, HFFRs 2-({9-[(4, 6-diamino-1, 3, 5-triazin- needed (no great cost increase) and polymer
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dripping/flow while burning is reduced. The composite OH• + H2 + PO• → H2O + HPO
may have multifunctional performance (ex: electrical HPO2• + H• → H2O + PO
conductivity from carbon nanotubes) and a balance HPO2• + H• → H2 + PO2
between flammability and mechanical properties may be HPO2• + OH• → H2O + PO2
maintained. However, careful design and analysis is
required for set up of a polymer nanocomposite structure. 4. Application of Flame retardants
Many aspects of nanocomposite technology (long-term Polycarbonates and Their Blends:
ageing, environmental hazards, conservation of fire safety At least in the last decade, patents published on the flame
principles etc.) are not known. retardancy of polycarbonates (PCs) and their blends
 Synergist: The most widely used antimony synergist significantly exceed the number of patents on flame
is antimony trioxide, antimony pentoxide & Sodium retardancy of any other polymers. Bridged aromatic diphenyl
antimonate phosphates, especially resorcinol bis (diphenyl phosphate)
 Antimony Trioxide: Approximately 20,000 metric tons and bisphenol A bis (diphenyl phosphate) have found broad
of [1309-64-4] (commonly referred to as antimony application because of their good thermal stability, high
oxide), Sb2O3, was used in the United States in 1990 to efficiency and low volatility.
impart flame retardancy to plastics. Although antimony Aromatic phosphates are rarely used in plain PC because of
trioxide is found in nature, it is too impure to be used. partial loss of clarity, tendency to stress-cracking, and
Flame-retardant grades of antimony oxides are somewhat reduced hydrolytic stability, but are broadly used in
manufactured from either antimony metal or PC/ABS. Bridged aromatic diphenyl phosphates seem to be
the sulfide ore by oxidation in air at 600-800 °C. finding much broader application than monophosphates
 Antimony Pentoxide: The second most widely used because of good thermal stability and low volatility.
antimony synergist is antimony pentoxide [1313-60- Resorcinol bis (diphenyl phosphate) available from Supresta
9], Sb2O5, produced by the oxidation of the trioxide using LLC under the trade name Fyrolflex RDP
either a peroxide or nitric acid. Antimony pentoxide is Gajiwala et al. [28] synthesized and characterized the two
available as a nonpigmenting colloidal suspension in thermally stable polymers containing a polybenzimidazole
either water or organic media or as an agglomerated and a ladder polymer structure are described. The
powder. polybenzimidazole polymer was synthesized by condensing
 Sodium Antimonate: Sodium antimonate [15593-75- tetra amino phenazine with terephthaldehyde in dimethyl
6], Na3SbO4, another antimony synergist of commercial acetamide solvent.
importance, has an antimony content of 61-63 wt % and a Chen et al. [29] synthesized a novel silicone and phosphate
bulk density of 39.4-46.4 kg/m3. It is made by oxidizing modified acryl ate (DGTH) and characterized by 1H NMR
antimony trioxide using sodium nitrate and caustic. and FTIR. Zuo et al. [30] synthesized a novel phosphorus-
containing triazine oligomers poly (2-morpholinyl-4-
3. Mechanism pentaerythritol phosphate-1, 3, 5-triazine) (PMPT) as a kind
Since the understanding of flame retardancy mechanisms of of tri-component intumescent flame retardant (IFR).
flame retardants containing phosphorus tends to be Rakotomalala et al. (2010) [31] synthesized the latest
oversimplified, in this subsection some details are underlined. advancements in phosphorus containing flame retardants for
Some general points about fire retardancy mechanisms will be electrical and electronic (EE) applications and compare them
clarified in advance, with the following subsection with commercially available ones. The mechanism of
concentrating on more specific results and conclusions with degradation and flame retardancy of phosphorus flame
respect to the tasks and materials investigated. retardants in epoxy resins will also be discussed.
In a very similar way to the flame retardants containing Adivarekar et al. (2013) [32] synthesized halogen free
halogen; those containing phosphorus can act in the gas phase ecofriendly phosphorous based flame retardant for
[11, 24]
. In this case hydrogen and hydroxy radicals are replaced polypropylene.
by less effective radicals or are rendered harmless by radical
recombination in the gas phase. Some key reactions, of the Polyesters and Nylons
hundreds possible, are proposed to be the most important Non-halogenated systems are of interest for polyesters and
(Equation 1). Branching and chain reactions of the oxidation nylons and a few have recently been introduced to the market,
of hydrocarbons in the gas phase are slowed down or whereas nonhalogen phosphorus-based additives, thermosol
interrupted, which is called flame inhibition, and reduces the finish, or co-reactant systems have been in use for many years
production of heat. The efficiency of P in the gas phase is in PET textiles [33]. The requirements for polyesters and
reported to be similar or even superior to hydrogen halides nylons are stringent because of high processing temperatures,
like HBr [24] Although detailed investigations of the flame sensitivity to degradation caused by possible acids and the
zone, such as identifying the intermediate products and need for long-term dimensional stability, and avoidance of
monitoring concentrations of the different products, are rather exudation (‘blooming’). These various requirements have
rare [25, 26, 27] the main principle seems to be understood. It is eliminated most of the known phosphorus-based flame
believed that the PO-radical plays the major role. retardants apart from thermally very stable materials. In late
Furthermore, the resulting flame retardancy effects are 70s and early 80s, various metal salts of dialkylphosphinates
obvious, including a clearly decreased heat release due to a were prepared at and tested in PET by Pennwalt [34]. Later,
reduced heat release rate (HRR)/mass loss rate value during Ticona and Clariant [36-38] following up this invention as well
flammability and fire tests. as earlier work by Hoechst [35] tested a variety of
PO• + H• → HPO dialkylphosphinates; zinc, aluminum, or calcium salts in
PO• + OH• → HPO2 glass-filled nylons and polybutylene terephthalate (PBT).
HPO + H• → H2 + PO• They found that the Al or Ca salts of ethylmethylphosphinic

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Acid. group and phenol formaldehyde novolac (n-PF). All the cured
Thach-Mien et al. [39] developed an environmentally friendly EPND/ HMMM/n-PF hybrid resins achieved the UL 94 V-0
halogen-free phosphorus–nitrogen bond flame retardant for grade with high limited oxygen indices (LOI>45.7). It is
cotton fabrics A novel flame retardant diethyl 4- found that phosphorous and nitrogen elements in the cured
methylpiperazin-1-ylphosphoramidate (CN-3) containing EPN-D/HMMM/n-PF hybrid resins had a positive synergistic
phosphorous and nitrogen was prepared. effect. Gérard et al. [55] prepared the flame retardant epoxy-
Thach-Mien et al. [40] synthesized a new charring agent, a based thermosets. The incorporation of additives in these
derivative of cyanuric chloride, mono-substituted, dimethyl polymers, including synergism effects. Reactive flame-
(4,6-dichloro-1, 3, 5-triazin-2- yloxy) methyl phosphonate retardantswhich are incorporated in the polymer backbone-are
(CN), was synthesized in good yield and characterized. Its reported and the use of fire-retardant epoxy coatings for
flame retardant and thermo gravimetric properties were materials protection is also considered.
compared to those of the di-substituted compound, tetra Tomuta et al. [56] synthesized Dihydrazides of different
methyl (6-chloro-1, 3, 5-triazine-2, 4-diyl) bis (oxy) bis structure. And tested as curing agents for DGEBA epoxy
(methylene) diphosphonate (CN-1). coatings. By calorimetric studies their latent characteristics
were proved and the kinetics of the curing studied.
Epoxy resins Gouri et al. [57] synthesized phosphazene compound like
There are a few ways to incorporate phosphorus-containing Cyclotriphosphazene containing the epoxy group
species into the epoxy resin network, some of which are hexaglycidyl cyclotriphosphazene (HGCP). This reactive
finding commercial application [41]. Since the P–H bond can monomer that is inherently flamed retarding contain P and N,
add to the epoxy group, this reaction can be used to attach can be used on their own as composite material precursor or
hydrogen phosphonates or phosphinates to an epoxy resin. added to current bulk commercial polymer diglycidylether of
The only example of a commercially available reactant of this bisphenol A (DGEBA) to enhance flame retardancy. The
type is the DOPO mentioned previously. It is sold in Japan, thermal stability and flame retardancy of HGCP thermosets
China, and Europe and is recommended to be a part of the with MDA curing agent and its blend as flame retardant with
curing system for halogen-free flame-retardant epoxies [42]. DGEBA were checked by the UL-94 vertical test.
However, it has a drawback related to its monofunctionality Meenakshi et al. [58] developed and characterized triphenyl
and can only be used in conjunction with other curing agents. phosphine oxide based phosphorus tetraglycidyl epoxy
By reacting DOPO with quinone, a phenolic difunctional nanocomposites denoted as ‘C’ and to find out its suitability
product can be made. This product is available in Japan from for use in high performance applications. Rane et al [59] are
Sanko. It can be incorporated in an epoxy resin through a synthesized phosphorous containing amine, tripropyldiamine
chain-extension process similar to tetrabromobisphenol A. phosphine oxide and hybrid monomer 4-(N-
Although it provides good physical properties and the pthalimidophenyl) glycidyl ether & characterized by FTIR,
required level of flame retardancy, it is not finding broad NMR & elemental analysis.
application because of its price.
Phosphine oxide structures have been proposed to impart Polyurethane (Pu) Foams An oligomeric ethyl phosphate
flame retardancy to curing agents, because phosphine oxides additive containing 19% phosphorus has been introduced by
are thermally and hydrolytically very stable. Many studies Supresta LLC as Fyrol PNX. It is an Oligomeric additive [91,
92]
have been reported in the literature concerning the curing of with a repeating unit of the structure.
epoxy resins with bis (aminophenyl)-methylphosphine oxide, Because PNX is halogen-free, it is especially of interest in
as well as thermal and combustion performance of the fire- Europe, particularly with respect to the automotive industry
retardant epoxies [43-49]. and their low fogging/volatile organic content (VOC)
Because of the strong nucleophilic character of the amino emission requirements. In the MVSS 302 test, this oligomer is
groups, it cures epoxy at the relatively low temperature of on average 40-50% more efficient than the chloroalkyl
150°C. Recently, Great Lakes patented a broad range of OH phosphates. In terms of VOC, PNX compares well with other
functional triphenyl or diphenylalkyl phosphine oxides [50]; flame retardants used in the automotive industry, but it
however, probably for price reasons, they seem to be becomes especially advantageous because the low use level
concentrating on the mixture of tri-, di- and mono-functional also helps to maintain low VOC.
4-hydroxyphenyphosphine oxides [51]. Yang Cao et al. [60] are synthesized four excellent halogen-
Ru-Jong et al. [52] synthesized Flame retardant epoxy free biphosphonate flame retardants (EBDMP, EBDEP,
polymers based on all phosphorus-containing epoxy resin, bis MBDMP, MBDEP). They are synthesized through
(3-t-butyl-4-glycidyloxyphenyl-2, 4-di-t-butylphenyl) polycondensation and Arbuzov rearrangement reactions
resorcinol diphosphate, and subsequently cured with non- without using any solvents. The products were characterized
phosphorus containing amines, and/or novel phosphorus by ESI-MS, FT-IR and 1H NMR. The application of EBDEP
containing aromatic or polyoxy alkylene amines. in polyurethane soft foam was studied and the results
Zhang et al. [53] synthesized a novel bisphenol 1, 4’-bis{4-[(4- illustrated its excellent flame-proofing properties
hydroxy) phenyliminomethylidene] phenoxy} benzene
(BHPB), which contains azomethine moiety and flexible 5. Conclusion
aromatic ether linkage, was synthesized and introduced into The scientific and public debate on flame retardants has led to
the curing system composed of diglycidyl ether of bisphenol some regulatory restrictions on mostly halogenated flame
A (DGEBA) and diamine. retardants (e.g. RoHS and WEEE directives, REACH in
Huang et al. [54] prepared flame-resistant novel halogen-free Europe) as well as the evaluation of alternatives. The
epoxy hybrid hexakis (methoxy methyl) melamine (HMMM), researcher confirmed that, viable alternative flame retardants
a phosphorous containing epoxy resin (EPN-D) with 9, 10- are available, HFFRs have similar fire performance and
dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) technical application capabilities as BFRs. In general, halogen

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free systems produce less smoke and less toxic components in profiles of chemicals flame retardant, alternatives for low
smoke. Flame retardants manufacturers try to develop new density polyurethane foam. (Report). EPA 742-R-05-
and better products as well as supply their customers with all 002A, 2005.
necessary information. 13. Xiao Y, Zheng Y, Wang X, Chen Z, Xu Z. Preparation of
From the commercial standpoint, phosphorous flame a Chitosan Based Flame-Retardant Synergist and Its
retardants are in active state of development driven by their Application in Flame-Retardant Polypropylene. Journal
good performance & also by environmental & regulatory of Applied Polymer Sciences, 2014, 1-8.
problem with the brominated flame retardants. Reactive 14. Li G, Wang W, Cao S, Cao Y, Wang Y. Reactive,
polymeric phosphorous base flame retardants are under active Intumescent, Halogen-Free Flame Retardant for
development in epoxy printed wiring board to replace TBBA. Polypropylene. Journal of Applied Polymer Science,
On the scientific side, enough mechanism of action research 2014.
has been carried out to show that while non-halogenated 15. Kim J, Nguyen C. Thermal stabilities and flame
flame retardant like phosphorous flame retardant can have an retardancies of nitrogen-phosphorus flame retardants
important mode of action as char former or char enhancer in based on bisphosphoramidates. Polymer Degradation and
the condensed phase, there is increasing recognition that Stability. 2008; 93(6):1037-1043.
vapor phase action can be significant as the existence of these 16. Wu DH, Zhao PH, Liu YQ, Liu XY, Wang XF. Halogen
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