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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.
373
374
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?
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.
375
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.
376
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
377
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
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
378
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
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
379
380