A Brief Review on

Organophosphorus Flame Retardants

Dr. G. Chandra Sekhar Reddy

 Since the implementation of environmental directives banning or limiting the use

of halogenated compounds, the development of flame retardants has focused on
more environmentally friendly alternatives.
Phosphorus compounds have received a growing attention from both industry and
academic community.
The range of phosphorus-based flame retardant products is extremely wide,
including
phosphates,
phosphonates,
phosphinates,
phosphine
oxides,
phosphates and red phosphorus.
These phosphorated flame retardant agents can be used as additives or
incorporated into the polymer chain during its synthesis, and are known to be
active in the condensed and/or vapor phase.
In the condensed phase, the phosphorus-based flame retardants are particularly
effective with polymers containing oxygen (polyesters, polyamides, cellulose,
etc.).
With most of them, thermal decomposition leads to the production of phosphoric
acid, which condenses readily to produce pyrophosphate structures and liberate
Atwater.
high temperature, ortho- and pyrophosphoric acids are turned into
metaphosphoric acid (O)P(O)(OH) and their corresponding polymers (PO3H)n.
The phosphate anions (pyro- and polyphosphates) then take part, with the
carbonized residues, in char formation.
This carbonized layer (char) isolates and protects the polymer from the flames and:
- limits the volatilization of fuel and prevents the formation of new free-radicals;
- limits oxygen diffusion, which reduces combustion;
- insulates the polymer underneath from the heat.

Phosphorus flame retardants (PFRs)

The polymers prepared showed initial decomposition

temperatures above 340 C, excellent thermal stability, high char
yields at 850 C and very high limited oxygen index (LOI) values
of 5659.
The polymers char yields and their (P+Si) contents showed
linear relationships.

 Polymers were prepared from reacting various diols with DPDCS, as

shown in below scheme, with stoichiometric feeding ratios to yield
PES-I or
with imbalanced stoichiometric feeding ratios, i.e., with a 15%
excess of aromatic diols to yield OES-I, OES-II, and OES-III as
detailed in Table 1.

Scheme

1:

Preparation

of

Table 1: Preparation and characterization of

polyaryloxydiphenylsilane polymers

Figure 1: FTIR
spectra of PES-I
and OES-II.

Figure 2: The plot of polymers

char yields (700 C in air) versus
polymers (P+Si) contents.

Figure
3:
TGA
thermograms
of
the
polyaryloxydiphenylsilanes
Table 2: Thermal properties of polyaryloxydiphenylsilane
polymers

IDT = initial decomposed temperature,

IPDT = integral procedural decomposition
temperature
The low melting points of the OES polymers
implied that they are easily processed with

molten processes, especially while the OES polymers are used as flame retardants for

o New star-shaped phosphorus-containing flame retardants were synthesized by

phospha-Michael-addition of diphenylphosphine oxide (DPhPO) and dimethyl
phosphite (DMP) to oligofunctional acrylates.
o The products were examined via UL 94 V-rating and thermogravimetric analysis in
three different epoxy resin systems: (i) RTM6, (ii) the two-component RTM system
bisphenol A diglycidyl ether (DGEBA) and (iii) an epoxy novolak resin (Dow
DEN438) cured with dicyandiamide (DICY) as hardening agent and 1,1-dimethyl-3phenylurea (fenuron) as accelerator, a three-component system predominantly
used for prepreg applications, i.e. for printed wiring boards.
o The influence of a systematically altered chemical environment of the phosphorus
atom on the flame retardancy and the char yield was investigated.
o Furthermore, the glass transition temperatures of the modified resins were studied

(A)

(B)

Scheme 2: Synthesis of DPhPP (1), DPhPI (2), DOPP (3), DOPI (4), DMPP
(5), and DMPI (6).

Table 3: Molecular weight, phosphorus content, and chemical

environment of the phosphorus atom for DPhPP (1), DPhPI (2), DOPP
(3), DOPI (4), DMPP (5), and DMPI (6)

The compounds 16 were blended into the epoxy resins with phosphorus
contents between 1.0 and 3.0% depending on the system and processed
as described above.

Table 4: UL 94-V screening and glass transition temperatures for RTM6

blended with 16. Neat resin: n.c.; Tg: 229 C

Table 5: UL 94-V screening and glass transition temperatures for DGEBA

cured with DMDC, blended with 16. Neat resin: n.c.; Tg: 172 C

Table 6: a. UL 94-V screening and glass transition temperatures for epoxy

novolak (DEN438) cured with DICY and fenuron, blended with 14. Neat
resin: n.c.; Tg: 182 C

b. UL 94-V screening and glass transition temperatures for epoxy novolak

(DEN438) cured with DICY and fenuron, blended with 5 and 6. Neat resin:
n.c.; Tg: 182 C

High Performance Polymers, 00: 000000, 2010

DOI:10.1177/0954008309353951

Phosphorus-containing Polysulfones A
Thorsten HoffmannStudy
Doris Pospiech, Liane Huler, Karin Sahre, hartmut
Comparative
,

Komber, Christina Harnisch, Maria Auf Der Landwehr

Leibniz-Institut fr Polymerforschung Dresden e.V., Hohe Str. 6, 01069,
Dresden, Germany

Alexander Schfer, Manfred Dring

Research Center Karlsruhe GmbH, Institute of Technical Chemistry, 76021,
Karlsruhe, Germany
Aromatic phosphorus-containing polysulfones (P-PSU) are reported.
The properties of these polymers are compared to bisphenol A-based
polysulfones.
Both diols have the phosphorus unit as substituent and differ in the
number of oxygen atoms within the environment of the phosphorus
changing

from

DOPO-HQ

(phosphinate

structure

to

DPPO-HQ

(phosphine oxide structure).

The use of DPPO-HQ decreased the number of side reactions and

Scheme 3: Synthesis route for the preparation of the phosphorus-containing P-PSU (PPSU_A, P-PSU_B)
Polysulfones (PSU), Phosphorus-Polysulfones (P-PSU)

ATRFTIR in-line monitoring

technique

Figure 4: Plots of ATR-FTIR spectra in

the spectral region of 1050 to 1350
cm-1 (a) and in the spectral region of
900 to 700 cm-1 (b) taken during the PPSU_A polycondensation in NMP.
During the synthesis of P-PSU_A, the
growth of the polymer chains is
indicated by the appearance of the
aromatic COC ether band at 1243
cm-1 (Figure 3a).
Otherwise,
the
disappearance
of
characteristic monomer bands of
DFDPS at 713 cm-1 and DOPOHQ at
781, 755 and 713 cm-1 is clearly
observed in the spectral region below
900 cm-1.
However, the CF bands (DFDPS) at 835
and 818 cm-1 are strongly overlapped
by bands of solvent (NMP) and newly

Table 7: Chemical and thermal characterization of phosphorus-containing P-PSUs in

comparison with PSU.

Figure 5: TGA of P-PSU_A (dotted line) and of P-PSU_B (dashed line) in comparison
with the neat PSU (solid line) in nitrogen atmosphere.

Figure 6: Decomposition of PSU (solid line), P-PSU_A (dotted line), and P-PSU_B
(dashed line): heat release rate as function of temperature obtained by pyrolysis
combustion flow calorimeter.

 The pyrolysis and fire behavior of halogen-free flame-retarded DGEBA/DMC, RTM6 and their
corresponding 60 vol.-% carbon fibers (CF) composites were investigated.
A novel phosphorous compound (DOPI) was used. Its action is dependent on the epoxy matrix.
Only flame inhibition occurs in the gas phase. RTM6 shows flame inhibition and a condensed
phase interaction increasing charring.
Both mechanisms decrease with increasing irradiance, whereas in RTM6-CF charring is
suppressed at low ones.
RTM6+DOPI shows a higher LOI (34.2%) than DGEBA/ DMC+DOPI and a V-0 classification
in UL 94.
Adding CF only enhances the LOI, DOPI+CF leads to a superposition in LOI for
DGEBA/DMC-CF+DOPI (31.8%, V-0) and a synergism for RTM6-CF+DOPI (47.7%, V-0).

Dopac-3-isocyanurate [DOPI]

Scheme 4: a) Synthesis of DOPI. b) Components of DGEBA/DMC. c) Main

components of RTM6.

Table 8: Investigated materials. The amount of CF corresponds to 60 vol.-%. And glass transition
temperatures, Tg (3 Hz), of the investigated materials with an error of 2K.

All thermosets containing 2 wt.-% of phosphorus in the final product were

prepared
The decrease in Tg is attributed to a reduction in the effective number of
crosslinking points per volume, mainly due to the replacement of epoxy
resin by the flame retardant as modification

Figure 7: Mass and mass loss rate of (a) DGEBA/DMC (filled squares) and DGEBA/DMC+DOPI
(open squares) and (b) RTM6 (filled circles) and RTM6+DOPI (open circles) under nitrogen at a
heating rate of 10 K min-1.

The reduction in thermal decomposition temperature is attributed to the

lower crosslinking density of the systems or the ester group within the flame
retardant, respectively.
Table 9: Thermal analysis of DGEBA/DMC, DGEBA/DMC+DOPI, RTM6 and RTM6+DOPI (ML= mass
loss).

Table 10: Time to ignition (tig) of the investigated materials, LOI

results and UL 94 results for a sample thickness of 3.0mm.
In agreement with results
received in pyrolysis it is
concluded
that
both
flammability
tests
are
influenced by gas phase and
condensed
phase
mechanisms.
While a gas phase mechanism
betters the LOI in both
materials,
the
additional
action
of
DOPI
in
the
condensed
phase
of
RTM6+DOPI changed melt
flow properties in the burning
zone and therefore flaming
dripping in the UL 94 was
suppressed.

Fire Behavior

Figure 8: (a) HRR and (b) THR of

DGEBA/DMC
(filled
squares),
DGEBA/DMC+DOPI (open squares),
RTM6 (filled circles) and RTM6+DOPI
(open circles) at an external heat flux
of 50 kW.m-2.

Cone
calorimeter
measurements at different
external heat fluxes

Figure 9: (a) PHRR, (b) THE, (c) THE/ML

and (d) residue of DGEBA/DMC (filled
squares),
DGEBA/DMC+DOPI
(open
squares),
RTM6
(filled
circles)
and
RTM6+DOPI (open circles) at different
external heat fluxes.

Fire Behavior

Figure 10: (a) HRR and (b) THR of

DGEBA/DMC-CF (filled triangles) and
DGEBA/DMC-CF+DOPI (open triangles)
and RTM6-CF (filled inverse triangles)
and RTM6-CF+DOPI (open inverse

Cone
calorimeter
measurements at different
external heat fluxes

Figure 11: (a) PHRR, (b) THE, (c)

THE/ML and (d) residue of DGEBA/DMCCF
(filled
triangles),
DGEBA/DMC
CF+DOPI (open triangles), RTM6-CF
(filled inverse triangles) and RTM6CF+DOPI (open inverse triangles) at

Table 11: Results of cone

calorimeter measurements at
different external heat fluxes for
all investigated materials
(PHRR = peak of heat release
rate,
THE = total heat evolved,
THE/ML = effective heat of
combustion of the volatiles
multiplied by the combustion
efficiency,
tig = time to ignition).
The values are averaged from
two measurements.

 With the introduction of phosphorus containing segments, polyester

onset weight-loss temperatures in both nitrogen and air are enhanced.
Thermal degradation kinetics were analyzed and which showed a
decreased activation energy for the co-polyester compared with that for
neat Poly(trimethylene terephthalate) (PTT), strongly suggesting that
the increased onset weight-loss temperature in nitrogen is a result of
enhanced carbonization.
Improved flame-retardant properties of co-polyester were observed

Scheme 5: Synthesis of PTTEP via solid-state

polymerization.
Table 12: PTT and PTTEPs
polymers.
The actual
phosphorus
content of the
purified copolyester was
determined using
oxygen flask
combustioninductively coupled
plasma atomic
emission

Figure 12: TG curves of PTT and PTTEPs at the heating rate of 10 C/min in N2 (a)
and air atmosphere (b)
Table 13: TG and DTG results of PTT and
PTTEPs.

Thermal combustion properties of PTT and PTTEPs were characterized by

microscale combustion calorimetry (MCC).

Figure 13: HRR curves of PTT and

PTTEPs at 1 C/s heating rate in N2.

Figure 14: PHRR and THR value of

PTT and PTTEPs at 1 C/s heating
rate in N2.

Microscale combustion calorimetry was carried out to test the

flammability behavior of the co-polyester.

Thermal degradation kinetics were

analyzed using the FlynnWall
Ozawa method.

Figure 15: TG curves of PTT and

PTTEP30 at different heating rates in
N2.

Figure 16: Ozawa plots of PTT and

PTTEP30 at following fractional weight
losses (): 0.05, 0.10, 0.15, 0.20 and
0.35.
Showing correlation coefficient above 0.99; thus
indicating the applicability of this
method to the present system.

Table 14: Activation energy of PTT and PTTEPs using the FlynnWallOzawa
method.

Pyrolysis GCMS
Figure 17: GC traces for the
evolved products of PTT and
PTTEP30 during pyrolysis

DOPOHQ-HE does not significantly

change the pyrolysis products of
the samples, with benzoic acid,
methyl vinyl terephthalate and
diallylterephthalate accounting for
65% of all the pyrolysis products.
PTTEP30, however, exhibited a
greater
number
of
chromatographic peaks than was
observed with the degradation of
neat PTT. This difference can be
attributed to the introduction of
phosphorus
containing
flame
retardant. DOPO-HQ-HE has a
different chemical structure than
PTT, thus can yield different

Conclusions
Phosphorus flame retardants generally act in both gas and condensed
phase. They can also be chemically tailored to favor one mechanism
or the other.
Unlike other halogen-free alternatives, phosphorus compounds have
demonstrated flame retardancy with relatively low loadings,
regardless of their mode of addition.
The altered bond nature between phosphorus and adjacent atoms
(oxygen and carbon) provoked different thermal stability and
consequently changed the decomposition mechanism.
High phosphorus contents led to polymers exhibiting high activation
energy of decomposition and leading as best flame retardants in
literature.
DOPO derivatives interest because they lead to excellent flame
resistance which is caused by the rapid decomposition of the DOPO
unit, accompanied by the release of dibenzofuran and a PO radical at
increased temperatures in the case of fire.
Hence, new multifunctional reactive DOPO derivatives (like, DOPO-

Conclusions
In the DOPO-HQ as well as DPPO-HQ the phosphorus is located in the
side chain and has differed only in the number of oxygen atoms
within the environment of the phosphorus. While the oxygen O1
bound to the P atom in the DOPO unit can interact with the OH-group
(O4) to form an intramolecular hydrogen bond able to disturb the
poly-condensation, the phosphine oxide structure in DPPO-HQ seems
more suitable for poly-condensation.

Such reactive DOPO derivatives or phosphorus containing oligomers

will also answer the problem of leaching that occurs with the use of
additive flame retardant.
In addition, efforts are currently invested towards developing new
halogen-free flame retardant systems investigating both new
phosphorus containing structures as well as synergism with other
existing inexpensive inorganic additives.

Thank
Thank
you
you