Alternative FR Plasticizers for Isopropylated TPPs, TCP and TXP and

other Flame Retardant Considerations

Paul Y. Moy Market Support Mgr., Plasticizers & FRs
ICL-IP America, Inc.
Ardsley, New York - USA
1-(914) 269-5942
Paul.moy@icl-ipa.com
st

61 IWCS Providence, RI
November 11th -14th 2012
Keywords: triaryl phosphates; alkyl diphenyl phosphates; Flame retardants
as a partial replacement for antimony oxide can
lead to lower heat release rates and effectively
lower the propagation potential for fire. Also, the
substitution of antimony oxide, well known for
increasing smoke development, may lessen the
evolution of smoke. One suspect mechanism
for this is by improving the char formation during
combustion by altering the surface morphology
to form a more cohesive dome. This dome can
prevents or lessen fissure cracks in the charring
layer and prevent the release of combustible
volatile gases.

Abstract:
Recent changes in European labeling has
renewed focus on product selection for flame
retardants such as flame retarding plasticizers
phosphate esters used in PVC and antimonybased synergists. The labeling change of
isopropylated TPP phosphate plasticizers and
other materials have drawn focus to the hazards
associated with these chemicals, especially in
open compounding processes such as roll mill
or calendering operations; better alternatives are
being considered. Antimony oxide, once a
preferred synergistic flame retardant additive for
vinyl, is a primary focus for replacement due to
its high costs and suspect health concerns
(dusting). Traditional alternatives have not
readily met the balance of properties offered by
these products.

Introduction:
For many years (and still to this day), flexible
elastomers usually were sourced from
Southeast Asia using organic sources (natural
latex). These materials were difficult to get
(especially in war time) and at an escalating
cost. Although PVC was discovered long before
it was a commercial success, finding the right
combinations of stabilizers and plasticizers to
render this resin useful as a flexible alternative
to rubbers did not come to fruition until the
1940s (1). These products were developed as a
needed replacement during the war efforts.

However, new options exist with similar

plasticization properties and more favorable
labeling. For flame retardant plasticizers, alkyl
diphenyl phosphates and blends with nontraditional triaryl phosphates can offer similar FR
performance and potentially lower smoke
evolution. Alternative plasticizers can offer lower
volatility ensuring longer contribution or viability
without compromising the flame retardancy of
the composite system.

Flexible vinyl was found to be an easy option

over convention rubber products as most of the
commercial equipment used for elastomeric
compounding could be easily adapted for
flexible vinyl composites. And, the vinyl process
could be done at a higher operating temperature
(with the right formulation of plasticizers,

Additionally, for more robust composites, careful

formulation (synergists/additives) work can offer
alternative means for effecting low combustion
behavior. The use of certain inorganic additives

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lubricants and stabilizers) allowing for faster and

higher yields of product. Rubber composites
were limited in process speeds due to concerns
for cross-linking/vulcanization.
One of the earliest plasticizer used for flexible
PVC was tricresyl phosphate (TCP). In addition
to being an excellent plasticizer, TCP was found
to be an excellent flame retardant as well. The
use of flame retarded vinyl composites with TCP
in wire and cable insulation worked very well
over then conventional elastomeric materials.
Insulation properties were as good or better than
natural elastomers and also much better in
aging resistance and flame retardancy. Flexible
vinyl was considerably more cost efficient and
readily available.

However, in the early days of flexible vinyl, the

process used for producing TCP plasticizers,
used natural cresols sourced from coal tar
derivatives. Unfortunately these coal tar
derivatives contained high levels of ortho-cresol,
a neurotoxin; the industry quickly looked for
alternatives.
Like TCP, cresyl diphenyl phosphate (CDP) and
trixylenyl phosphate (TXP) ester analogs were
found to have neurological activity due to the
coal tar raw material . Although each had
carved a niche into vinyl applications, the
industry sought alternative plasticizers for each
of these products.

Tricresyl phosphate was produced by the

following reaction scheme;

Figure 1: Synthetic route of Aryl Phosphate

Esters

The development of synthetic processes which

contained very low levels of the ortho isomer
was subsequently used as an alternative
feedstock. Now the production of tricresyl
phosphate includes the use of cresols with very
low levels of o-cresol (0.05%). Other
isomers, such as isopropylphenol and tbutylphenol were developed in the 60s which
were, at the time, found to be much safer and
economical to produce. These triaryl phosphate
products were similar to the TCP reaction
scheme, using other alkylphenol feedstock to
produce phosphate esters analogs.

For tricresyl phosphate, R would represent a

methyl group for the alkyl component, reacting
with phosphorus oxychloride (plus catalysts) to
form tricresyl phosphate. Other versions of
cresylic/xylyl phosphates would prove to be
useful as well.

In the early 60s, Ciba Geigy developed a series

of isopropylated phenol based (Reofos)
phosphate esters which could be used as a
direct substitute for each of these problematic
plasticizers. By varying the degree of alkylation,
the properties of the resultant analogs could
match physical and performance properties of
the three cresylic phosphates So, to match the
required viscosity range, substituting the
isopropylphenol at roughly seventy-five percent
would result in a product similar in properties to
tricresyl phosphate, at sixty-five percent
substitution cresyl diphenyl phosphate and
roughly ninety percent substitution is equal to
trixylenyl phosphate.(2) These products have
also been described as isopropylated triphenyl
phosphates (IPPP).

In the early development of FR vinyl composites,

phosphate esters were commonly used and
grew into three major versions of triaryl
phosphates:

Tri-Aryl Phosphate Types;

Trixylenyl phosphate (TXP) - low

volatility, useful for flexible agricultural
vinyl films (greenhouses) and light
stable and also is one of the prime flame
resistant hydraulic fluids still used today
in the marketplace.

Tricresyl phosphate (TCP) high

solvating general purpose flame
retardant plasticizer
Cresyl diphenyl phosphate (CDP)
similar to TCP but slightly more fugitive.

The industry continues to prefer these

substituted Isopropylphenyl analogs to the

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Proceedings of the 61st IWCS Conference

the phosphate esters, E-modulus values were

determined (composite strain at 100%
elongation). Here comparable formulations
show, as expected, TCP to be slightly more
efficient than isopropylated TPP and TBPP to be
slightly less yet.

original cresylics to this day. However, due to

recent results disclosed from the European
REACH initiative, the health and ecological
effects rescreening of these plasticizers have
shown greater hazards than previously thought.
As a class, the isopropylated triphenyl
phosphates have raised their concern to a more
severe reproductive, developmental and STOT
(specific target organ toxicity) classification. So,
for open blending processes such as roll mill
operations, the operator is potentially exposed to
these products.

T-Butyl Analogs
Other plasticizers based on the tertiary
butylphenol platform may come into play for the
flexible vinyl market. One developmental
plasticizer (E09-31, ICL-IP) based on this
technology shows exceptionally better hydrolytic
stability, a common weakness for phosphate
esters while maintaining the same high degree
of flame resistance.

Discussion:
All the cresylics and isopropylated TPP
plasticizers have made a tremendous impact on
flame retarded PVC composites. For many wire
and cable composites, these flame retardant
plasticizers are major contributors to the FR
effectiveness of the compounds. Should they be
substituted, are there appropriate alternatives to
fill their place?

To measure the hydrolytic stability of these

plasticizers, a small quantity of each product
was combined in an aqueous solution and
placed in a vial subject to accelerated
temperature (70C) for up to a month exposure.
Two alkylated diphenyl phosphates and another
t-butylphenyl diphenyl phosphate were
evaluated. Titrated measurements for
developed acid number were recorded after
each week of exposure (four weeks total). The
results show the developmental phosphate ester
to be more hydrolytically stable under these
conditions (Table 3).

The short answer is yes. Although these two

classes of triaryl phosphates have had problems
with health and environmental issues, other
triaryl phosphate esters do not necessarily share
the same problems. An example of this is the
analog tertiary butylphenyl diphenyl phosphates
(TBPP). This class of plasticizers has not
shown reproductive nor organ sensitivity to the
extent of isopropylated TPPs and are readily
biologically degradable, thus much more
environmentally friendly as compared to IPPPs.

Application areas where stability has greater

value may benefit from this property.

Although the t-butylphenyl diphenyl phosphates

are not quite as effective as the cresylic and
isopropylated TPPs in terms of plasticizing
efficiency, they are essentially as FR efficient as
any other triaryl phosphate ester. As proof of
this, formulations with increasing levels (and
varied) of typical FR additives with fifty parts of
each phosphate ester plasticizer (TCP, IPPP &
TBPP) were measured for flame retardant
efficacy. The table (Table 2) below shows
virtually the same flammability values in almost
every comparison [as measured by LOI (Limited
Oxygen Index) and UL-94]. The formulation
used for these composites are referenced in
Table 1.

Blend Options
Most flexible vinyl composites are mixtures of
many different components and may (probably)
have more than one type of plasticizer. As
typical of phosphate ester composites, most
compounders formulated their products with
enough FR plasticizer to reach the desired
specification and balance the required
mechanical properties with lower cost
plasticizers. Hence the concept of offering
blends which have been engineered to give
excellent flame retardant properties while also
providing for the necessary plasticization. One
such blend is Phosflex 375 which is based on
the tertiary butylphenyl aryl phosphate esters
and has been shown to be an excellent
alternative plasticizer for isopropylated TPPs.
Using the same formulation scheme shown in
Table 1, the following comparisons of flame
retardant efficiency is demonstrated in Table 4.

In addition to the flammability properties, other

composite properties such as tensile and
hardness were measured (Table 2). Comparing
similarly formulated PVC compounds, the
differences or influence from each plasticizer are
shown. To quantify the plasticizing efficacy of

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There is very good agreement in most

composite formulations using the blended
plasticizer Phosflex 375 and the isopropylated
phosphates plasticizer.

FR Additives
The careful selection of plasticizers constitutes
one aspect of controlling flame retardancy; the
inclusion of inorganic additives is another route.
Antimony trioxide (ATO) is probably the first
choice as an FR additive for vinyl composites for
many compounders as it is very effective at a
low addition rate. Unfortunately, the current
price for this product is forcing composite
manufacturers to look for more cost-effective
alternatives. In addition to flame retardant
issues, low smoke performance is becoming an
important characteristic for passing local fire
codes and regulations.

Alkyl Aryl Phosphates:

Another alternative for triaryl phosphates could
possibly be alkyl diphenyl phosphates (ADPs).
These plasticizers are, in general, good flame
retardant plasticizers (not quite as FR efficient
as the triaryl phosphates) but possess the
property of low smoke generation and low
temperature flexibility (almost as good as
phthalate esters). For certain applications, low
smoke characteristics are often the much harder
value to achieve than the respective flammability
property. Test protocols like the ASTM E-84
Tunnel test are typical of the difficulty to meet
the smoke range but most times, relatively easy
to pass the flame spread rating.

One choice is a novel borate additive built on a

silicate support (FR1120) which has the
potential to at least partially replace antimony
oxide and also provide low smoke properties in
vinyl composites. Like other commercial
borates, the contribution from this additive also
produces a glassy dome type of surface
morphology. However, especially in calorimetry
type FR protocols where heat release
measurements are important, composites
containing this additive seem to form a more
effective, uniform and cohesive char layer on the
dome surface. This characteristic prevents or
lessens the phenomena of fissures or cracking
during combustion which releases combustible
gases causing excessive heat release spiking.
The net effect results in a decreased of heat
release values which could help pass the test.
(See Figures 3-4)

There are three types of ADPs (major

commercial products) used for flexible FR vinyl
compounds;
2-ethylhexyl diphenyl phosphate
Isodecyl diphenyl phosphate
Linear alkyl (c12-c16) diaryl phosphate
All three ADPs display low smoke characteristics
better than triaryl phosphates but what
separates one from the other is volatility. Figure
2 shows the relative volatility of these
plasticizers when held at 190deg C in an
isothermal TGA scan. The linear alkyl diphenyl
phosphate is clearly superior for volatility
characteristics.

Comparing ATH/Zn borate (Figure 2) to a

similarly formulated mixture ATH/Novel borate
additive (Figure 3), a more uniform char layer is
produced potentially lessening the chance of
fissures developing in the course of the burn
test.

Reference to a past technical paper(3) from

Monsanto (D. Paul et al) on alkylated diphenyl
phosphates speaks on the mechanisms of its
flame retardancy. It is suggested to produce a
more efficient char growth during combustion
due to the early formation of acid esters
accelerating the decomposition of the vinyl resin.
Further decomposition of the plasticizer forms
polyphosphoric acid which helps build the
integrity of the char and excludes oxygen from
the flame front. In comparison, triaryl
phosphates are believed to work more so in the
vapor phase hence the differences in smoke
characteristics between the two types of
phosphate esters.

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FR1120 is a non-zinc containing additive and

has shown to be more stable during vinyl
compounding scenarios than other zinc
containing additives like zinc borate.

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Proceedings of the 61st IWCS Conference

Author: Paul Moy

Currently serve as the Market Support Mgr for
Plasticizers and Flame Retardants at ICLIndustrial Products based in Ardsley, NY.

Conclusions:
As regulations change and new specifications
are put into place, this becomes an opportunity
to improve formulations and enhance the
performance profile of the composites. These
alternatives offer other benefits such as
enhanced low smoke capabilities, potentially
longer service life, all with a more sustainable
chemistry to protect our environment and the
safety of the consumers using these products.
Although slightly less plasticizing, tertiary
butylphenyl diphenyl phosphate ester
plasticizers can be a major component of highly
FR efficient vinyl composites. As for sustainable
chemistry, these plasticizers do not share the
same repro/tox profile as the isopropylated
analogs and other triaryl phosphates.
Similarly, the alkyl diphenyl phosphates are
known to have a better health profile than the
isopropylated triaryl phosphates and cresylic
phosphates previously mentioned. As an
alternative technology, ADPs offer unique
benefits to the polymer composites with low
smoke and low temperature flexibility while still
offering enough flame retardancy to pass flame
spread protocols. All of these technologies
described in this paper can be viable options for
safer, more sustainable and efficient vinyl
composites.

References:
(1) Encyclopedia of PVC 2nd Edition Vol.
4, R. Grossman Marcel Press NY, 1998,
Page 2
(2) Reofos 95, Reofos 65, Reofos 50
Triaryl phosphates plasticisers
brochure Ciba-Geigy -8/93
(3) A New Phosphate Plasticizer for Low
Smoke Wire & Cable Applications, D.
Paul, Monsanto Corporation - FRCA
Conference Coronado, CA October
1991

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Table 1: Formulations for Flexible Suspension PVC at 50 phr Plasticizer

Formula Ref.
PVC
CaCO3
Zinc Borate
Alumina trihydrate
Plasticizers
Epoxidized Soya Oil
Ba/Zn mixed metal stabilizer
totals:

1
100
50

2
100
50
3

3
100
50
6

50
3
5
208

50
3
5
211

50
3
5
214

4
100
50
3
20
50
3
5
231

5
100
50
6
40
50
3
5
254

Table 2: Flammability and Physical Properties of FR PVC Composites

FR
Component

Formula
Ref #

Additive(s)

Tensile Properties
E
Strength
Modulus
Elong.

Phr

(psi)

(psi)

Hardness

LOI

UL-94

Shore "A"
Creep
Initial
(15sec.)

O 2%
100
Mils

1.6mm

TCP
ZB
ZB
ZB/ATH
ZB/ATH

1
2
3
4
5

50
3
6
3/20
6/40

2200
2200
2200
1900
1900

980
1000
1040
1100
1190

420
420
383
337
335

93
94
94
94
96

89
90
89
90
92

31.2
32.2
32.6
33.4
36

V0
V0
V0
V0
V0

IPPP
ZB
ZB
ZB/ATH
ZB/ATH

1
2
3
4
5

50
3
6
3/20
6/40

1940
1906
1972
1713
1543

1128
1074
1118
1127
1170

305
314
324
286
242

92
92
92
92
93

88
88
87
88
90

30.4
31
31.6
32.8
35.5

V0
V0
V0
V0
V0

1
2
3
4
5

50
3
6
3/20
6/40

2202
2175
1949
1848
1882

1133
1139
1162
1228
1357

362
363
305
291
286

92
93
92
93
94

86
88
87
89
90

31
31.5
32.6
33.6
36

V0
V0
V0
V0
V0

TBPP
ZB
ZB
ZB/ATH
ZB/ATH

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Table 3 - Hydrolytic Stability of Phosphate Esters

Exposure (@ 70C)

Sample ID
ADP-1
ADP-2
TBPP
E09-31

1 week

2 weeks

3 weeks

4 weeks

Acid Number
mg KOH/g
0.049
0.028
0.094

Acid Number
mg KOH/g
0.062
0.032
0.122

Acid Number
mg KOH/g
0.083
0.039
0.160

Acid Number
mg KOH/g
0.098
0.046
0.196

0.016

0.020

0.026

0.029

Table 4: FR Comparison of Phosflex 375 vs. Triaryl Isopropylated TPP

Components

Formula #

Additive(s)

LOI (O2%)
100 Mils

UL-94
1.6mm

phr

Isopropylated TPP
ZB
ZB
ZB/ATH
ZB/ATH

1
2
3
4
5

50
3
6
3/20
6/40

30.4
31
31.6
32.8
35.5

V-0
V-0
V-0
V-0
V-0

Phosflex 375
ZB
ZB
ZB/ATH
ZB/ATH

1
2
3
4
5

50
3
6
3/20
6/40

30.5
30.8
31.7
32.5
33.7

V-0
V-0
V-0
V-0
V-0

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Figure 2: Isothermal TGA (190C) of Alkyl Diphenyl Phosphates

Linear alkyl diphenyl phosphate

Isodecyl diphenyl phosphate

2-etylhexyl diphenyl phosphate

Figure 3: ATH / Zn Borate

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Figure 4: ATH / Novel Borate

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