European Polymer Journal 48 (2012) 15611574

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Are novel aryl phosphates competitors for bisphenol A bis(diphenyl

phosphate) in halogen-free ame-retarded
polycarbonate/acrylonitrilebutadienestyrene blends?
Eliza Wawrzyn a, Bernhard Schartel a,, Michael Ciesielski b, Bernd Kretzschmar c,
Ulrike Braun a, Manfred Dring b
a
b
c

BAM Federal Institute for Materials Research and Testing, Unter den Eichen 87, 12205 Berlin, Germany
Institute of Technical Chemistry, KIT Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany

a r t i c l e

i n f o

Article history:
Received 27 April 2012
Received in revised form 22 June 2012
Accepted 25 June 2012
Available online 3 July 2012
Keywords:
Polycarbonate (PC)
Aryl phosphate
Flame retardancy
Pyrolysis
PC/ABS

a b s t r a c t
The reactivity of the ame retardant and its decomposition temperature control the condensed-phase action in bisphenol A polycarbonate/acrylonitrilebutadienestyrene/polytetrauoroethylene (PC/ABSPTFE) blends. Thus, to increase charring in the condensed
phase of PC/ABSPTFE + aryl phosphate, two halogen-free ame retardants were synthesized:
3,3,5-trimethylcyclohexylbisphenol bis(diphenyl phosphate) (TMC-BDP) and bisphenol A
bis(diethyl phosphate) (BEP). Their performance is compared to bisphenol A bis(diphenyl
phosphate) (BDP) in PC/ABSPTFE blend. The comprehensive study was carried out using
thermogravimetry (TG); TG coupled with Fourier transform infrared spectrometer (TGFTIR); the Underwriters Laboratory burning chamber (UL 94); limiting oxygen index
(LOI); cone calorimeter at different irradiations; tensile, bending and heat distortion temperature tests; as well as rheological studies and differential scanning calorimeter (DSC).
With respect to pyrolysis, TMC-BDP works as well as BDP in the PC/ABSPTFE blend by
enhancing the cross-linking of PC, whereas BEP shows worse performance because it
prefers cross-linking with itself rather than with PC. As to its re behavior, PC/ABSPTFE +
TMC-BDP presents results very similar to PC/ABSPTFE + BDP; the blend PC/ABSPTFE + BEP
shows lower ame inhibition and higher total heat evolved (THE). The UL 94 for the materials with TMC-BDP and BDP improved from HB to V0 for specimens of 3.2 mm thickness
compared to PC/ABSPTFE and PC/ABSPTFE + BEP; the LOI increased from around 24% up to
around 28%, respectively. BEP works as the strongest plasticizer in PC/ABSPTFE, whereas
the blends with TMC-BDP and BDP present the same rheological properties. PC/ABSPTFE +
TMC-BDP exhibits the best mechanical properties among all ame-retarded blends.
2012 Published by Elsevier Ltd.

1. Introduction
Bisphenol A bis(diphenyl phosphate) (BDP) and resorcinol bis(diphenyl phosphate) (RDP) are effective halogen-free ame retardants for bisphenol A polycarbonate/
acrylonitrilebutadienestyrene (PC/ABS) blends [15].
Oligomeric aryl phosphates combine gas-phase and
Corresponding author. Tel.: +49 30 81041021.
E-mail address: bernhard.schartel@bam.de (B. Schartel).
0014-3057/$ - see front matter 2012 Published by Elsevier Ltd.
http://dx.doi.org/10.1016/j.eurpolymj.2012.06.015

condensed-phase modes of action [68]. They act as a

scavenger of H or OH radicals in the ame and initiate
cross-linking reactions within the pyrolysis zone [9,10]. It
was pointed out that the increasing decomposition
temperature of commercially available aryl phosphates
such as triphenyl phosphate (TPP), RDP and BDP increases
their activity in the condensed phase of PC/ABS/polytetrauoroethylene (PC/ABSPTFE) blend [11]. Increasing the
overlap between decomposition temperature ranges increases the probability for reactions between the ame

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retardant and PC decomposition products [11]. In other

words, correspondence between the decomposition
temperature range of aryl phosphate and the PC/ABSPTFE
decomposition is a prerequisite for enhanced charring in
the condensed phase. Additionally, the ame retarding
action of phosphates depends on the reactivity of the compound used [12]. More reactive aryl phosphates increase
the activity in the condensed phase due to more cross-linking with PC.
The aim of this work was to enhance charring in the
condensed phase of PC/ABSPTFE + aryl phosphate. To reach
this goal two approaches were proposed:
(1) increasing the decomposition temperature of the
aryl phosphate beyond the decomposition temperature of BDP,
(2) using aliphatic derivatives of bisphenol A phosphate
to increase the cross-linking activity due to the early
scission of the aliphatic groups.
Thus, so far only two patents [13,14] mentioned novel
ame retardants were synthesized: 3,3,5-trimethylcyclohexylbisphenol bis(diphenyl phosphate) (TMC-BDP) and
bisphenol A bis(diethyl phosphate) (BEP), showing a higher
decomposition temperature and higher char yield, respectively. TMC-BDP, BEP and BDP were incorporated in PC/
ABSPTFE and compared to each other using thermal analysis
(TG), ammability (LOI, UL 94), re behavior (cone calorimeter at different external heat uxes), mechanical tests
(tensile test, bending test and heat distortion temperature
test) as well as rheological test and differential scanning
calorimeter (DSC). TMC-BDP is proposed as an interesting
alternative to BDP.
2. Experimental section
2.1. Synthesis of aryl phosphates
All materials and reagents used for the reactions were
purchased from Aldrich and used without any further
purication. 1H and 31P nuclear magnetic resonance spectroscopy (NMR) spectra were obtained using a Bruker
AC-250 Spectrometer at 250 MHz. Tetramethylsilane and
trimethyl phosphate, respectively, were used as internal
standards. Samples were analyzed in deuterated DMSO.
The melting point was measured using the melting point
apparatus Bchi B-545 at heating rate of 3 K min 1. The
elemental analysis was carried out using a Vario EL III from
Elementar Analysensysteme GmbH. The purity of obtained
aryl phosphate was studied by means of high-performance
liquid chromatography (HPLC) using HP 1100 Hewlett
Packard. The mobile phase consisted of acetonitrile/water,
ow rate was 1 ml/min and the monitoring wavelength
was 254 nm.
2.2. Preparation of the blends
The synthesized aryl phosphates and BDP were incorporated into PC/ABSPTFE using a co-rotating twin-screw extruder Micro 27 (Leistritz, Nuremberg). PC/ABSPTFE and BDP

were provided by Bayer MaterialScience AG (Dormagen,

Germany). The extruder has a screw diameter of 27 mm
and a length of 36 D. The pellets of PC/ABSPTFE were predried for 3 h at 373 K and fed into the hopper. The liquid
TMC-BDP and BEP, heated up to 383 K, were introduced
into barrel 4 at 14 D length at 523 K. Gravimetric dosing
systems were used in both cases. The following processing
parameters were applied: an increasing temperature program from 503 K to 523 K, a screw speed of 200 rpm and
a throughput of 10 kg/h. The extruded strands were pelletized after cooling in a water bath.
The cone calorimeter specimens were manufactured
from pellets using an Allrounder 420 C 1000-250 injection
molding machine (Arburg, Germany) with a cylinder diameter of 35 mm and clamping force of 1000 kN. The specimens for LOI and UL 94 and the multipurpose test
specimens (ISO 3167 type A) for the mechanical tests were
molded using a machine Ergotech 100/420-310 (Demag,
Germany) with cylinder diameter of 30 mm and clamping
force of 1000 kN and a two-cavity mold. In both cases,
sample molding was done according to CAMPUS conditions. An increasing temperature program up to 523 K
was used, the injection speed was 40 mm/s and the mold
temperature was set at 353 K.
The composition of studied blends is given in Table 1.
All investigated samples consisted of unbranched polycarbonate based on bisphenol A. PTFE masterbatch was added
as an antidripping agent in the ratio 1:1 of styreneacrylonitrile (SAN) copolymer and neat PTFE. The ABS ratio was
21:13:66 and its particles were embedded within the
homogenous PC matrix phase. The ABS exhibited a core
shell structure, since butadiene rubber particles were
grafted with SAN. The molecular weight of BDP, if consisting of one repeating unit, was MwBDP = 696.6 g/mol. The
oligomeric BDP investigated had an average repeating unit
of n = 1.1 and contained about 2.5% of TPP. For the ameretarded PC/ABSPTFE blends the same amount of aryl phosphate was always applied (10 wt.%). This means that the
blends had different phosphorus content (Table 1).

2.3. Characterization
The pyrolysis experiments were performed using TG on
a TGA/SDTA 851 (Mettler Toledo, Germany) under nitrogen
and a heating rate of 10 K min 1. The sample mass was
10 mg for each measurement. FTIR spectrometer Nexus
470 (Nicolet, Germany) was coupled with TG to analyze

Table 1
Composition of investigated blends in wt.% (remaining wt.% is other
additives).

PC
ABS
PTFE
BDP
TMC-BDP
BEP
P-content

PC/ABSPTFE

PC/ABSPTFE +
BDP

PC/ABSPTFE +
TMC-BDP

PC/ABSPTFE +
BEP

81.14
17.14
0.52

73
15.42
0.46
10

73
15.42
0.46

73
15.42
0.46

10
0

4.3

3.9

10
7.7

E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

the pyrolysis gases. The temperature of the transfer line

was held constant at 523 K and that of the gas cell at
533 K during each measurement.
The forced aming behavior of the blends was investigated using cone calorimeter (FTT, UK) following ISO
5660 under three irradiations: 35, 50 and 70 kW m-2. The
sample size was (100  100  4) mm. The specimens were
wrapped in aluminum foil and placed horizontally in the
frame under the cone heater at a distance of 35 mm. The
ammability (reaction to the small ame) was determined
according to the UL 94 test for the ammability of plastics
by vertical (V2, V1, V0) and horizontal (HB) classications
following IEC 60 695-11-10, and according to LOI following
ISO 4589-2. The dimensions of the specimens for the UL 94
test were (120  12.5  1.6) mm and (120  12.5  3.2)
mm; those for LOI test were (127  6.5  3.2) mm.
For rheological investigations the rheometer Anton Paar
Physica MCR 301 was used, with plateplate geometry, a
gap of 1 mm and a plate diameter of 25 mm. Isothermal
measurements were conducted in the frequency sweep
mode at the following temperatures: for PC/ABSPTFE and
PC/ABSPTFE + BDP at 473 K, 498 K, 543 K and 588 K; for
PC/ABSPTFE + BEP at 473 K, 498 K and 543 K; for PC/ABSPTFE + TMC-BDP at 498 K, 543 K and 588 K. The frequency
was varied between 100 Hz and 0.1 Hz and a small deformation (gamma = 0.5%) was chosen. All measurements
were taken in a nitrogen environment. The master-curves
of the materials were determined with the reference
temperature of 498 K.
The glass transition temperature (Tg) was determined
using the differential scanning calorimeter (DSC) performed on a DSC 7020 (Mettler Toledo, Germany). The following parameters were applied: the temperature
program between 203 K and 523 K, three times heating
and two times cooling, both at a rate of 10 K min-1, and a
nitrogen ow of 50 ml min-1. The sample mass was 5 mg.
The mechanical properties were determined using
tensile, bending and heat distortion temperature tests.
For tensile tests a Zwick UPM 1456 universal testing machine (Zwick Ulm, Germany) was used; bending tests were
conducted on a UPM zwicki 2,5 (Zwick Ulm, Germany)
according to ISO 527 and ISO 178, respectively. The charpy
impact strength tests were carried out on PSW 25 J testing
equipment (WPM Leipzig GmbH, Germany) with respect to
ISO 179 and the heat distortion temperature was determined using HDT 3/Vicat (CEAST, Italy) according to ISO
75 under 0.45 MPa load. The tests were carried out at room
temperature and the data obtained represented the average value from 10 test specimens.
The determination of phosphoric acid content of neat
aryl phosphates as well as the molecular weight distributions of PC/ABSPTFE + aryl phosphate blends were carried
out using gel permeations chromatography (GPC) with a
PSS SDV column (5 lm, ID 8.0 mm x 300 mm), dichloromethane as an eluent at a ow rate of 1.0 ml/min. This
GPC system was operated at 296 K using a PSS SECcurity
1200 HPLC pump and a PSS SECcurity 1200 Differential
Refractometer RID detector. The concentration of the
sample solutions was about 5.0 mg/ml. The samples were
completely dissolved by stirring at about 313 K overnight.
The calculation of the average molecular weights and the

1563

molecular weight distribution of the samples was carried

out by the so-called slice by slice method based on the
polystyrene (PS) calibration.

3. Results and discussion

3.1. Synthesized ame retardants
Two ame retardants were synthesized: TMC-BDP and
BEP. TMC-BDP were obtained in two-step reactions
(Fig. 1a and b), and BEP in one step (Fig. 1c).
3,3,5-trimethylcyclohexylbisphenol (TMC; Fig. 1a):
Phenol (1000 g, 10.64 mol), dodecylthiol (35.8 g, 0.18
mol) and dihydroisophorone (3,3,5-trimethylcyclohexan1-one) (248 g, 1.77 mol) were placed in a stirring apparatus, equipped with a stirrer, thermometer, reux condenser and gas inlet pipe. The system was heated to
301 K and dry hydrogen chloride (HCl) gas was added
slowly while stirring over a period of 5 h at a temperature
of 301303 K. The mixture was left to react overnight at
room temperature. Then it was stirred again for 1 h at a
temperature of around 303 K. Next the water (1.5 l) was
added to the reaction mixture and a pH value of 6 was adjusted by adding a 45% solution of sodium hydroxide
(NaOH). The system was stirred again for 1 h at 353 K
and afterwards cooled down to room temperature. The
resulting crude product was ltered off and washed three
times with hot water (353 K). Then the residue was hot-extracted with hexane and twice with methylene chloride
(CH2Cl2). The product was recrystallized from xylene and
left to dry under air at ambient temperature. The yield
was 77%. Using this procedure a total of around 900 g
TMC was obtained. The white product had a melting point
of 482485 K (literature: 482485 K [15]) and was used
without further purication. TMC was characterized with
1
H NMR (Fig. 2a). Spin multiplicity is indicated: singlet, duplet, triplet, quartet and multiplet. The chemical shifts in
TMC are given in the following: 1H NMR (DMSO, ppm):
d = 0.31 (s, 3H), 0.92 (overlapped signals: s, 6H and m,
2H), 1.29 (d, 1H), 1.71 (d, 1H), 1.86 (m, 1H), 2.41 (d, 1H),
2.58 (d, 1H), 6.59 (dd, 4H), 7.03 (dd, 4H), 9.06 (bs, 2H).
TMC-BDP (Fig. 1b): TMC (200 g, 0.65 mol) and tetrahydrofuran (THF, 364 ml) were lled into a three-necked
round-bottomed ask equipped with a stirrer, thermometer, inert gas pipe and dropping funnel. When TMC was
dissolved, the triethylamine (182 ml) was added and the
reaction mixture was cooled down to 278 K using an ice
water bath. Then, diphenyl chlorophosphate (364 g,
1.35 mol) was fed into the reaction mixture via a dropping
funnel over a period of 5 h in an inert atmosphere in the
temperature range from 278 K to 282 K. After introducing
diphenyl chlorophosphate, the reaction system was stirred
overnight at ambient temperature. The obtained triethylammonium chloride was ltered off and washed with
tert-butyl methyl ether (3  90 ml). The combined organic
phases were extracted with 1 N solution of sodium hydroxide (NaOH, 3  100 ml) and with water (1  100 ml). The
remaining organic layer was dried with magnesium sulfate
(MgSO4), ltered off and evaporated. Next, the crude product was dissolved in CH2Cl2 (182 ml) and extracted once

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

Fig. 1. Synthesis route of (a) TMC, (b) TMC-BDP and (c) BEP.

more with 1 N of NaOH (3  100 ml) and with water

(1  100 ml) in order to thoroughly remove impurities.
The organic phase was dried, ltered and evaporated. The
product yield was 73%. Using this procedure a total of
around 2240 g of TMC-BDP was obtained. The purity of isolated TMC-BDP was over 98% and was established by HPLC
detection in which the main peak was eluted at 23.273 min
(data not shown). TMC-BDP was characterized with 1H
NMR (Fig. 2b) and with 31P NMR. 1H NMR (DMSO, ppm):
d = 0.29 (s, 3H), 0.94 (overlapped signals: s, 6H and m,
2H), 1.31 (d, 1H), 1.83 (overlapped signals: d, 1H and m,
1H), 2.57 (d, 1H), 2.78 (d, 1H), 7.05-7.48 (overlapped signals, 28H); 31P NMR (DMSO): d = 15.93 ppm. Elemental
analysis of TMC-BDP gave the following results: C
68.71 wt.%, H 5.67 wt.%. P 7.86 wt.%; Calculated: C

76.25 wt.%, H 5.97 wt.%, P 8.74 wt.%. The molecular weight

of TMC-BDP, if consisting of one repeating unit, was
MwTMC-BDP = 712.4 g/mol. The oligomeric TMC-BDP investigated had an average repeating unit of n = 1.1. The elugram
showed before the main TMC-BDP peak a small signal from
larger oligomer. The obtained TMC-BDP is free of byproducts and impurities, particularly no phosphoric acid was
found using GPC measurements.
The synthesis of BEP (Fig. 1c) was performed similar to
the synthesis of TMC-BDP, at a temperature of 278282 K
using bisphenol A (45.6 g, 0.2 mol) and diethyl chlorophosphate (70 g, 0.4 mol) as reagents and THF (122 ml) as the
solvent. Triethylamine (56 ml) was applied as an auxiliary
base. Diethyl chlorophosphate was introduced into the
reaction mixture over a period of 1.52 h at a temperature

E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

1565

Fig. 2. 1H NMR of (a) TMC, (b) TMC-BDP and (c) BEP.

between 278 K and 282 K, and afterwards the system was

left to react overnight at room temperature while stirred.
The resulting residue was washed with tert-butyl methyl
ether (3  25 ml). An organic layer was extracted with
1 N solution of NaOH (3  30 ml) and with water

(1x30 ml). The product layer was separated and dried with
MgSO4. The MgSO4 was ltered off and the solvent was removed by heating to around 373 K at reduced pressure.
The extraction procedure was not repeated. The yield
was 81%. In this way around 700 g of BEP was obtained.

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

Fig. 3. Mass and mass loss rate of BDP (stars), TMC-BDP (triangles) and BEP (circles), under N2, heating rate = 10 K min

Table 2
Thermal analysis of BDP, TMC-BDP and BEP (under N2, heating rate
10 K min-1).

T2wt% /2 K
Tmax /2 K
Weight loss/1 wt.%
Residue/1 wt.%

BDP

TMC-BDP

BEP

592
735
96.1
3.9

644
759
97.3
2.7

512
582
82.2
17.8

The purity of BEP was over 90% and BEP was eluted at
7.337 min using HPLC (data not shown). BEP was characterized with 1H NMR (Fig. 2c) and with 31P NMR. 1H NMR
(DMSO, ppm): d = 1.25 (t, 12H), 1.61 (s, 6H), 4.12 (q, 8H),
7.01 (d, 4H), 7.23 (d, 4H); 31P NMR (DMSO): d = 5.04 ppm.
Elemental analysis of BEP gave the following results: C
54.68 wt.%, H 6.77 wt.%. P 12.24 wt.%; Calculated: C
57.77 wt.%, H 5.85 wt.%, P 12.84 wt.%. The molecular
weight of BEP, if consisting of one repeating unit, was
MwBEP = 500.4 g/mol. The oligomeric BEP investigated had
an average repeating unit of n = 0.95 and contained about

1.7% of phosphoric acid. The elugram showed before the

main BEP peak a small signal from larger oligomer.
The other characteristic of the synthesized ame retardants was achieved using thermogravimetry. The TG results of BDP, TMC-BDP and BEP are shown in Fig. 3 and
Table 2. All of the aryl phosphates decomposed in single
decomposition step with the maximum mass loss rate
(Tmax) at 735 K for BDP, 759 K for TMC-BDP and 582 K for
BEP. Additionally, for BEP a broad shoulder was observed
before (500550 K) and after (600650 K) the decomposition step. BEP began decomposing rst and left 17.8 wt.%
of residue. BDP decomposed at 592 K and yielded 3.9 wt.%
of residue, whereas TMC-BDP started to decompose at
644 K and its residue was 2.7 wt.%. TMC-BDP was more
stable than BDP. According to the rst approach of this
study, TMC-BDP in PC/ABSPTFE increases the overlap of both
decomposition areas, possibly enabling stronger interactions between ame retardant and the rearranged PC
structure. BEP showed the enhanced charring action in
comparison to both BDP and TMC-BDP. With respect to

Fig. 4. Mass and mass loss rate of PC/ABSPTFE (line), PC/ABSPTFE + BDP (stars), PC/ABSPTFE + TMC-BDP (triangles) and PC/ABSPTFE + BEP (circles) under N2,
heating rate 10 K min 1.

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

Table 3
Thermal analysis of PC, ABS, PC/ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP and PC/ABSPTFE + BEP (under N2, heating rate 10 Kmin-1).

T2wt%/2 K
Mass loss proceeds from BEP decomposition
Tmax/2 K
Weight loss/1.0 wt.%
1st main decomposition: ABS
Tmax/2 K
Weight loss/1.0 wt.%
2nd main decomposition: PC
Tmax/2 K
Weight loss/1.0 wt.%
Residue at 1000 K
Mass/1.0 wt.%
Calculated residue
Mass/1.0 wt.%

PC

ABS

PC/ABSPTFE

PC/ABSPTFE + BDP

PC/ABSPTFE + TMC-BDP

PC/ABSPTFE + BEP

752

655

675

665

657

582

585
6.9

688
97.3

715
25.6

700
25.0

700
22.4

703
26.9

798
72.2

770
55.2

794
51.2

785
55.9

798
43.7

27.8

2.7

19.2

23.8

21.7

22.5

17.7

17.6

19.1

the second motivation, more reactive BEP increases the

probability of networking with PC during decomposition.
3.2. Pyrolysis of PC/ABSPTFE+aryl phosphate: Mass loss
Three aryl phosphates were blended with PC/ABSPTFE
and compared with each other and with non-ame-retarded PC/ABSPTFE blend. Thermal analysis of PC/ABSPTFE,
PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP, PC/ABSPTFE + BEP
is shown in Fig. 4 and Table 3. Additionally Table 3 presents thermogravimetry results of neat PC and ABS. PC
and ABS decomposed in single step with the maximum
decomposition temperature (Tmax) at 769 K and 688 K,
respectively. PC yielded 27.8 wt.% residue and ABS
2.7 wt.%. Compared to PC and ABS, for PC/ABSPTFE the ABS
decomposition is shifted to higher and the PC to lower
temperatures indicating interactions between the components and resulting in a strong overlap of the decomposition ranges [6], whereas adding aryl phosphate increases
the separation of the decomposition ranges of the two
components again due to the interaction between the aryl
phosphates and PC. Nevertheless, the blends PC/ABSPTFE,
PC/ABSPTFE + BDP and PC/ABSPTFE + TMC-BDP decomposed
in principle in only two more or less overlapping decomposition steps dominated by the ABS and the PC
decomposition, respectively, whereas PC/ABSPTFE + BEP

showed an additional minor step originating from BEP

decomposition before the two major decomposition steps
occur. Furthermore, the mass loss after the minor decomposition step from PC/ABSPTFE + BEP is lower than the total
content of ame retardant in this blend. It means that BEP
did not decompose and vaporize completely. For all investigated blends, the rst main decomposition step was
attributed to ABS decomposition and the second main step
to PC decomposition.
The blend with BEP began decomposing much earlier
(582 K) than other investigated blends, whereas the following materials decomposed in the similar temperature
range of 657675 K: PC/ABSPTFE, PC/ABSPTFE + BDP and PC/
ABSPTFE + TMC-BDP. All ame-retarded blends shifted the
ABS decomposition step to lower temperatures than PC/
ABSPTFE. However, the PC decomposition step for ame-retarded blends was stabilized compared to PC/ABSPTFE. In
thermal analysis, addition of the ame retardants to PC/
ABSPTFE led to higher residue than that of single PC/ABSPTFE
blend. The residue increased in the following order: PC/
ABS PTFE < PC/ABS PTFE + TMC-BDP < PC/ABSPTFE + BEP < PC/
ABSPTFE + BDP. For ame-retarded blends the residues were
higher than residues calculated on the basis of superimposing the char yields of the individual ame retardants
(BDP, TMC-BDP and BEP) and simple PC/ABSPTFE. All investigated ame retardants work at least partly in the

Fig. 5. FTIR spectra at the minor decomposition step (580 K) of PC/ABSPTFE + BEP with the characteristic bands used for product identication originating
from diethyl hydrogen phosphate, ethylene, bisphenol A.

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

Fig. 6. (a) FTIR spectra of the rst main decomposition step of PC/ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP and PC/ABSPTFE + BEP with characteristic
bands used for product identication originate mainly from ABS. (b) FTIR spectra of the second main decomposition step of PC/ABSPTFE, PC/ABSPTFE + BDP,
PC/ABSPTFE + TMC-BDP and PC/ABSPTFE + BEP with characteristic bands used for product identication originate from PC.

condensed phase by enhancing char formation. The difference between experimental and calculated residue for
ame-retarded blends showed that BDP increased the
charring of PC/ABSPTFE by around 6 wt.%, TMC-BDP by
around 4 wt.% and BEP by 3.4 wt.%. In fact, BDP and TMCBDP showed the same enhancement of charring, taking
into account the 10 wt.% lower phosphorus content for
TMC-BDP in comparison to BDP, and the margin of uncertainty (1 wt.%). Besides BEP being more reactive than BDP
(and having a much higher phosphorus content), it
enhanced PC charring less than did BDP and TMC-BDP in
PC/ABSPTFE blend. Considering the residue obtained for
neat BEP, it is proposed that BEP release and self-charring
compete with the reactions with PC in PC/ABSPTFE + BEP
blend.
3.3. Pyrolysis of PC/ABSPTFE+aryl phosphate: Volatile products
The TG-FTIR analysis of the volatile pyrolysis gases of
PC/ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP, PC/
ABSPTFE + BEP is presented in Figs. 5 and 6.

Minor mass loss from BEP decomposition in PC/ABSPT+ BEP blend (585 K = 29 min, Fig. 5) showed absorption
bands such as P = O from phosphate at 1239 cm-1, POC
at 1045 cm-1 and POH at 1285 cm-1. These vibrations,
together with stretching vibrations from aliphatic groups
(CH2, CH3) between 2950 and 2880 cm-1, correspond
well to phosphate derivatives created during decomposition of BEP (Fig. 7). One of decomposition products from
BEP is diethyl hydrogen phosphate whose FTIR spectrum
(taken from database) ts well to vibrations observed at
minor decomposition step from PC/ABSPTFE + BEP. Furthermore, the FTIR analysis of the PC/ABSPTFE with BEP detected
absorptions of hydrogen attached to unsaturated carbon
atom (C = CH2) in the range between 3150 and 2990 cm-1
for stretching vibrations and at 19501820, 1443, 1420,
and at 1005890 cm-1 for deformation vibrations. Those
absorptions t well with the values for ethylene (Fig. 5).
Additionally, the following stretching vibrations are observed: at 1597 and 1495 cm-1 from CAr = CAr, at 3652 cm1
from CArOH, at 1168 cm-1 from CArO and at 3070 cm-1
from the aromatic ring CArH. These absorptions originated
FE

E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

1569

Fig. 7. Evolved gases observed in FTIR spectra at the minor decomposition step during thermal analysis of PC/ABSPTFE + BEP.

from phenol derivatives like bisphenol A (Fig. 5). The

results conrmed that BEP decomposed to bisphenol A,
ethylene and various phosphate derivatives, which may
further undergo decomposition releasing ethylene (Fig. 7).
At the rst main decomposition step (between 700 and
715 K = 4042 min) the analysis of pyrolysis gases via FTIR
of PC/ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP,
PC/ABSPTFE + BEP (Fig. 6a) showed stretching and deformation vibrations of aliphatic components RCH2R, RCH3
between 29502880 cm-1 and at 1447 cm-1, respectively,
stretching vibrations of styrene derivatives at 3070 and
3029 cm-1 by the aromatic ring CArH, at 1630 cm-1 by
the unsaturated side groups H2C = CH, at 1597 and
1495 cm-1 by the the aromatic ring CAr = CAr, and at 760,
870, 910, 982 cm-1 from deformation vibrations by the aromatic ring CArH. The particular absorption band of butene
was given at 912 cm-1 [16], and overlapped with the deformation vibration of CArH. These results corresponded to
the literature, where it is reported that ABS mainly decomposes into aliphatic compounds originating from butadiene
and styrene monomers and its derivatives, such as dimers,
trimers, methyl styrene and toluene [17,18]. Additionally,
at the rst main decomposition step of all investigated
blends absorptions from PC decomposition were observed
such as vibrations at 3650, 1244, and 1167 cm-1 of CArOH
from phenol derivatives, at 1747 cm-1 of the carbonyl
group C = O, at 2361 and 669 cm-1 vibrations of carbon
dioxide (CO2). These results conrmed that at the rst
main decomposition step of PC/ABSPTFE, PC/ABSPTFE + BDP,
PC/ABSPTFE + TMC-BDP and PC/ABSPTFE + BEP, the ABS
decomposed and PC started decomposing as well.
The major decomposition products monitored for the
second main decomposition step of all investigated blends
(between 770 and 798 K = 4750 min) (see Fig. 6b) were

CO2 (2361 and 669 cm-1), methane (CH4, 3015 and

1305 cm-1), carbon monoxide (CO, 2178 cm-1) and phenol
derivatives (3650 cm-1 from CAr-OH, 1597 and 1495 from
CAr = CAr, 1240 and 1175 cm-1 from CArO), which t very
well with the decomposition products of PC described in
the literature created via hydrolysis of carbonate linkage
and chain scission of isopropylidene linkage [1921]. For
PC/ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP and
PC/ABSPTFE + BEP the FTIR spectra of the second main
decomposition step revealed the decomposition of PC.
3.4. Pyrolysis: Enhancement of PC charring
The main decomposition pathways for PC during pyrolysis are KolbeSchmitt and Fries rearrangements, chain
scission of isopropylidene linkages and hydrolysis of carbonate linkage [22,23]. PC is a charring polymer [11]. Self
cross-linking of PC stabilized the polymer and promotes
charring [23,24]. ABS decomposed with only a very small
amount of residue, which did not contribute to charring.
Combining PC with BDP, TMC-BDP and BEP in PC/ABSPTFE
blends induced additional charring by cross-linking those
aryl phosphates with PC (Fig. 8). Supported by the presence
of PTFE, BDP, TMC-BDP and BEP created hydrogen aryl
phosphates which reacted with rearranged PC via transesterication reaction; consequently charring is enhanced
and improved. Improvement of PC charring was related
to the changed chemical structure of the residue of PC/
ABSPTFE + aryl phosphate in comparison to PC/ABSPTFE.
BDP and TMC-BDP underwent similar cross-linking reactions with PC and increased PC charring equally, taking
the different phosphorus content into account. The
situation for BEP was different. BEP decomposed to various
phosphate derivatives, which was observed in the gas

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

phase (Figs. 5 and 7). However, not all phosphates were

evolved. Some of it rapidly underwent polycondensation,
creating hydrogen polyphosphate. Self cross-linking of
BEP in PC/ABSPTFE was estimated to be the major reaction
of this ame retardant in the condense phase. Less
cross-linking of BEP to PC was detected, due to the fact
that the highly reactive BEP decomposed much earlier than
PC.

3.5. Fire performance: Forced-aming behavior and

ammability
Fig. 9 displays the heat release rate (HRR) of the
PC/ABSPTFE blends with and without ame retardants at
an external heat ux of 50 kW m-2. The HRR patterns for
PC/ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP and
PC/ABSPTFE + BEP were typical for charring and deformation

Fig. 8. Transesterication reactions between PC and (a) BDP, (b) TMC-BDP, (c) BEP in the condensed phase during thermal decomposition of PC/
ABSPTFE + aryl phosphate; R1 and R2 = H, CH2CH3, C6H5.

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

Fig. 9. Heat release rate (HRR) of PC/ABSPTFE (squares), PC/ABSPTFE + BDP

(triangles), PC/ABSPTFE + TMC-BDP(stars), PC/ABSPTFE + BEP (circles)
(irradiation = 50 kW m 2).

materials with the maximum HRR (pHRR) after the initial

increase when a char layer is formed [25,26]. The HRR
curves for PC/ABSPTFE + BDP and PC/ABSPTFE + TMC-BDP
showed no differences within the margin of uncertainty.
Among all ame-retarded blends, the material with BEP
has less good char. Char decomposition began earlier for
PC/ABSPTFE + BEP than for PC/ABSPTFE + BDP and PC/ABSPTFE + TMC-BDP. All investigated blends showed strong
deformation phenomena during cone calorimeter tests,
which resulted in high margin of error in pHRR for all
external heat uxes and time to ignition (tig) for
35 kW m-2.
The characteristic values of forced-aming behavior
were determined using the cone calorimeter at different
external irradiations and are summarized in Table 4.

The pHRR determines re propagation. The highest

pHRR was observed for the blend PC/ABSPTFE at all applied
irradiations, because of the lack of gas-phase action and
less effective char formation. The addition of the ame
retardants to PC/ABSPTFE blend reduced the pHRR. In
general, similarly strong reductions are observed for the
blend with BDP and TMC-BDP up to around 39% and 36%,
respectively. For the blend with BEP, the pHRR was
reduced to around 24% for the highest heat ux in comparison to the non-ame-retarded blend.
Total heat evolved (THE), which is the total heat released at ame-out, was reduced for ame-retarded blends
in comparison to PC/ABSPTFE at the highest irradiation. The
highest reduction was observed for the blend with BDP
(around 24%) and TMC-BDP (around 21%). Adding BEP to
PC/ABSPTFE blend reduced the THE by around 12.5%
(70 kWm-2). The materials with BDP and TMC-BDP yielded
very similar THE for all heat uxes applied, whereas the
blend with BEP showed worse results than other ame-retarded blends.
The residue of all blends investigated in cone calorimeter for 35, 50 and 70 kW m-2 lay in the same range considering uncertainty. However, the blend PC/ABSPTFE + BEP
tends to give the lowest residue among all investigated
blends, and the blend PC/ABSPTFE + BDP tends to higher residue formation than PC/ABSPTFE, PC/ABSPTFE + TMC-BDP and
PC/ABSPTFE + BEP.
Total heat evolved (THE) divided by mass loss (ML) is an
effective heat of combustion (THE/ML) and allows the gasphase activity to be determined by means of ame inhibition. Phosphorus ame retardants create the several types
of phosphorus radicals that react with highly reactive H or
OH radicals during combustion [9,27]. This strongly limits

Table 4
Cone calorimeter results (at ame out) and ammability (THE = total heat evolved, ML = mass loss, TCOP = total CO production, TCOP/ML = CO yield, TSR = total
smoke release, TSR/ML = smoke yield, pHRR = peak of heat release rate, tig = time to ignition).
PC/ABSPTFE

PC/ABSPTFE + BDP

PC/ABSPTFE + TMC-BDP

PC/ABSPTFE + BEP

Cone calorimeter (irradiation = 35 kW m )

pHRR/57 kW m 2
519
THE/5 MJ m 2
86.4
Residue/5 wt.%
26.3
THE/ML/0.1 MJ g-1 m-2
2.5
TCOP/ML/0.01 gg-1
0.06
TSR/ML/6 g-1
97

335
74.2
26.3
2.1
0.10
129

382
74.8
26.3
2.1
0.10
125

426
87.2
19.6
2.3
0.08
111

Cone calorimeter (irradiation = 50 kW m 2)

pHRR/110 kW m 2
593
THE/1 MJ m 2
92.6
Residue/7 wt.%
22.6
1
2
THE/ML/0.1 MJ g m
2.5
TCOP/ML /0.01 gg-1
0.06
TSR/ML /8 g 1
98

414
77.9
21.4
2.1
0.10
129

485
79.9
18.6
2.0
0.10
129

490
89.3
18.7
2.3
0.08
113

Cone calorimeter (irradiation = 70 kW m 2)

pHRR/42 kW m 2
762
THE/1 MJ m 2
97.9
Residue/1 wt.%
17.8
1
-2
THE/ML/0.1 MJ g m
2.5
TCOP/ML/0.01 gg 1
0.06
TSR/ML/3 g-1
101

463
74.2
21.8
2.0
0.09
141

488
77.1
18.1
2.0
0.10
138

582
85.7
16.4
2.2
0.09
116

Flammability
LOI/1%
UL 94 (3.3 mm)
UL 94 (1.6 mm)

27.9
V0
V0

26.5
V0
V1

23.5
HB
HB

23.9
HB
HB

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

the oxidation process and yields a lower heat release as a

consequence. The lower the THE/ML in comparison to
non-ame-retarded material is, the higher the ame inhibition of the ame retardant in the gas phase. For all blends
the THE/ML remained constant within the margin of error
for three applied external heat uxes. The highest THE/ML,
obviously, was obtained for the non-ame-retarded blend
PC/ABSPTFE. The lowest effective heat of combustion was
observed for the two blends PC/ABSPTFE + BDP and PC/
ABSPTFE + TMC-BDP. BDP and TMC-BDP reduced the THE/
ML by around 20% in comparison to simple PC/ABSPTFE,
which indicated efcient ame inhibition in the gas phase.
This ame inhibition is independent of the irradiation, and
thus constitutes the re retardancy. The blend with BEP
gave intermediate results, yielding a THE/ML higher than
the blends with BDP and TMC-BDP but lower than the
blend PC/ABSPTFE. The blend PC/ABSPTFE + BEP reduced the
THE/ML by around 12% compared to the non-ame-retarded blend. BEP worked worse than BDP and TMC-BDP
by means of ame inhibition.
The results for effective heat of combustion t well with
the results for effective carbon monoxide production
(TCOP/ML) and effective smoke release (TSR/ML). Carbon
monoxide (CO) and smoke are the products of incomplete
combustion. The lowest TCOP/ML and TSR/ML were obtained for PC/ABSPTFE blend. The highest TCOP/ML was
yielded by the blends PC/ABSPTFE + BDP and PC/ABSPTFE + TMC-BDP; hence the oxidation process for those
blends was strongly depleted. A similar trend was observed for TSR/ML.
The ammability results of both LOI and UL 94 for two
different thicknesses are presented in Table 4. The blends
PC/ABSPTFE and PC/ABSPTFE + BEP gave the same LOI results,
and neither passed the vertical burning test for two sample
thicknesses. Due to a long burning time they achieved HB
classication in UL 94. Adding BDP and TMC-BDP to PC/
ABSPTFE led to an LOI enhanced by around 4% and
gave the best UL 94 results (V0) for 3-mm specimens.
The 1.6-mm specimen of the blend with TMC-BDP gave a
V1 ratio, whereas the specimen of the blend with BDP
achieved the V0 class. Combining PC/ABSPTFE with BDP and
TMC-BDP led to a similar improvement in ammability.
Adding BEP to PC/ABSPTFE did not improve ammability
results compared to the non-ame-retarded blend.
3.6. Rheological properties, glass transition temperature and
mechanical properties
Not only the re retardancy of PC/ABSPTFE + aryl phosphate blends was investigated, the processing and
mechanical data were also determined using the rheological test, DSC and mechanical tests. The inuence of ame
retardants on the rheological properties of PC/ABSPTFE
blend is shown in Fig. 10. On this graph the shear stress
of four investigated materials was plotted as the function
of angular frequencies. All of the materials investigated
showed a ow limit due to the presence of PTFE in each
blend. The addition of PTFE to PC/ABS blends prevents
material from dripping [6]. Additionally, BDP, TMC-BDP
and BEP worked as plasticizers in PC/ABSPTFE blend. The
blends PC/ABSPTFE + BDP and PC/ABSPTFE + TMC-BDP had

Fig. 10. Rheological characteristics (shear stress as a function of angular

frequency) of PC/ABSPTFE (squares), PC/ABSPTFE + BDP (triangles), PC/
ABSPTFE + TMC-BDP (stars), PC/ABSPTFE + BEP (circles).

the same viscosity, whereas the blend with BEP exhibited

a stronger reduction in viscosity. The plasticizing effect of
the aryl phosphates is well known and constitutes a benet
for thermoplastic processing such as speeding up extrusion
and injection molding.
The results from rheological measurements correspond
to some extent with the results for the glass transition
temperatures (Tg) of the investigated materials (Table 5).
PC/ABSPTFE is a two-phase blend, showing two, clearly
separated glass transition temperatures. The rst Tg (Tg1)
originated from an ABS-rich phase; the second Tg (Tg2)
from a PC-rich phase. When 10 wt.% of ame retardants
was added to PC/ABSPTFE blend, both the Tg1 and Tg2
decreased in the following order: PC/ABSPTFE > PC/
ABSPTFE + TMC-BDP > PC/ABSPTFE + BDP > PC/ABSPTFE + BEP.
The smallest reduction in Tg1 and Tg2 was observed for PC/
ABSPTFE + TMC-BDP, since the TMC-BDP shows the highest
molecular weight of the investigated aryl phosphates and
a reduced molecular exibility due to the exchange of
the bisphenol A by 3,3,5-trimethylcyclohexylbisphenol.
The greatest reduction in Tg1 and Tg2 was observed for
PC/ABSPTFE + BEP and was most probably caused by the enhanced dynamics of the BEP achieved by replacing four
phenyl rings with four aliphatic groups, the reduced number of arylaryl interactions and the larger disturbance of
the molecular structure as opposed to BDP and TMC-BDP.
The enhanced dynamics contribute to the obvious decrease
in apparent viscosity in Fig. 10. Nevertheless, the different
order can indicate additional effects playing a role for the
viscosity, in particular for PC/ABSPTFE + BEP.

Table 5
Glass transition temperatures (Tg1 originates from the ABS-Rich phase and
Tg2 Originates from the PC-rich phase) of PC/ABSPTFE, PC/ABSPTFE + BDP, PC/
ABSPTFE + TMC-BDP, PC/ABSPTFE + BEP.

PC/ABSPTFE
PC/ABSPTFE + BDP
PC/ABSPTFE + TMC-BDP
PC/ABSPTFE + BEP

Tg1 /2 K

Tg2 /2 K

384
371
376
367

418
389
396
385

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E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

Table 6
Mechanical properties of PC/ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP, PC/ABSPTFE + BEP (HDT = heat distortion temperature, NB = No break).
TENSILE
Modulus (GPa)

PC/ABSPTFE
PC/ABSPTFE + BDP
PC/ABSPTFE + TMC-BDP
PC/ABSPTFE + BEP

2.16 0.11
2.51 0.09
2.37 0.16
2.40 0.16

BENDING
Elongation (%)
at Yield

at Break

5.1 0.1
4.1 0.1
4.2 0.1
3.5 0.4

109.5 1.6
60.6 40.0
81.4 36.6
4.6 3.0

The mechanical properties of all investigated materials

were studied by means of tensile, bending and heat distortion temperature (HDT) tests. Addition of ame retardants
to PC/ABSPTFE blend changed the mechanical properties as
summarized in Table 6.
Upon incorporation of 10 wt.% of ame retardants in PC/
ABSPTFE blend, the tensile modulus is increased around
12%. Taking into account the uncertainty there is no significant difference between adding the different aryl phosphates. The bending modulus increased in the order: PC/
ABSPTFE < PC/ABSPTFE + TMC-BDP < PC/ABSPTFE + BDP < PC/
ABSPTFE + BEP. Nevertheless, the increase (1013%) when
adding 10 wt.% aryl phosphates is clearly more signicant
than the differences between the different aryl phosphates.
Elongations at both the yield and the break decreased for
ame-retarded blends in comparison to PC/ABSPTFE. Among
ame-retarded blends the best results were obtained for
the blend with TMC-BDP, which reduced the elongation
at yield to around only 18% and elongation at break to
around 26% compared to the non-ame-retarded blend.
The highest reduction was observed for the blend with
BEP (31% reduction for elongation at break and 96% reduction from 109.5% to 4.6% for elongation at yield), indicating
that this material became very brittle compared to other
investigated blends. The reason for this extreme increase
in brittleness for PC/ABSPTFE + BEP was hardly only due to
disturbing the molecular structure and reducing interactions between matrix and BEP molecules through partly
replacing phenyl by aliphatic groups. A signicant reduction in molecular weight of PC was proposed that is also
hold responsible for the viscosity change beyond the physical plasticizing effect of BEP. The molecular weight of the
used PC was Mw = 27 000 Da. It is well known that a reduction in molecular weight to less than Mw = 22 000 Da
results in pronounced reduction in melt viscosity of PC
[28]. A reduction below Mw = 20 000 Da cuts in half
elongation to break and for Mw = 18 100 Da reduction in
elongation to break was reported to 4.7% accompanied by
a slight increase in modulus for PC [29], very similar as reported here for PC/ABSPTFE + BEP. In Table 7 Mw and Mn for
the polymer components the GPC signals for the ame
retardants occurred clearly separated and were not taken
into account for the data shown in Table 7 of the investigated blends are shown. The molecular weight distributions of the polymer components were asymmetric, but
did not show any multimodal characteristics itself for the
investigated blends. The molecular weight averages for
the blends are much higher than for the PC mainly due
to the ABS and the SAN/PTFE masterbatch contribution.

Modulus (GPa)

2.42 0.02
2.68 0.01
2.62 0.02
2.74 0.02

HDT
Charpy Impact Strength (kJm-2)
Unnotched

Notched

NB
NB
NB
198 82

65.3 4.4
19.2 2.0
19.5 1.1
7.5 1.9

(K)

380 1
363 1
364 1
353 1

Table 7
Molecular mass distribution (Mw and Mn) of the main polymer peak of PC/
ABSPTFE, PC/ABSPTFE + BDP, PC/ABSPTFE + TMC-BDP and PC/ABSPTFE + BEP.

PC/ABSPTFE
PC/ABSPTFE + BDP
PC/ABSPTFE + TMC-BDP
PC/ABSPTFE + BEP

Mn (Da)

Mw (Da)

22
21
20
18

47
47
44
39

400
300
600
500

900
700
400
600

Nevertheless the ranking as well as the order of magnitude

of the reduction in molecular weight prove the assumption. It is concluded that in contrast to PC/ABSPTFE + TMCBDP and PC/ABSPTFE + BDP signicant degradation of PC
was caused in PC/ABSPTFE + BEP by the phosphoric acid left
in the synthesized BEP during processing.
The Charpy impact strength test determines the amount
of energy per unit area that is absorbed by the material
during fracture. The results are analogous to the results discussed before for the viscosity, tensile investigation and
bending modulus. The unnotched specimens did not crack
at all except PC/ABSPTFE + BEP. The notched ame-retarded
specimens absorbed less energy during fracture than the
PC/ABSPTFE. The blends with TMC-BDP and BDP gave similar
clear reduction compared to PC/ABSPTFE in Charpy impact
strength tests, but in particular the blend with BEP required
very low energy to break.
The heat distortion temperature was reduced for the
blends with aryl phosphates in comparison to non-ameretarded blends. The strongest reduction in HDT was
observed for the material with BEP, whereas the blends
PC/ABSPTFE + TMC-BDP and PC/ABSPTFE + BDP gave similar
results. The results for the HDT correspond roughly with
the glass transition temperatures.
Mechanical tests showed that incorporation of TMCBDP, BDP and BEP decreased the toughness of PC matrix
in PC/ABSPTFE + aryl phosphate blends. In general, the best
results among all ame-retarded blends were obtained
for the material with TMC-BDP, whereas the material with
BEP became much more brittle.
4. Conclusion
The replacement of BDP in PC/ABSPTFE blend with the
synthesized aryl phosphates was studied in order to
enhance charring in the condensed phase of PC/
ABSPTFE + aryl phosphate by means of thermal analysis,
ammability, re behavior, mechanical tests, rheological
test and differential scanning calorimeter. Thus, two so
far only in patents mentioned novel ame retardants were

1574

E. Wawrzyn et al. / European Polymer Journal 48 (2012) 15611574

synthesized: TMC-BDP and BEP. Although TMC-BDP was

more stable than BDP and BEP yielded much more residue
in comparison to BDP, their incorporation into PC/ABSPTFE
blend did not enhance the ame retardancy in comparison
to PC/ABSPTFE + BDP.
All investigated ame retardants worked in the condensed phase of PC/ABSPTFE + aryl phosphate blends by
enhancing char formation and changing its structure.
Taking the different phosphorus content into account,
TMC-BDP worked as well as BDP in the PC/ABSPTFE blend;
both TMC-BDP and BDP reacted via transesterication between phosphate groups and phenolic groups of rearranged PC. BEP showed worse performance in the PC/
ABSPTFE blend. Some of the polyphosphate created during
BEP decomposition reacted with PC. However, since BEP
decomposed much earlier than PC/ABSPTFE blend, BEP preferred to cross-link with itself than with rearranged PC,
thus it did not enhance PC charring signicantly. Moreover,
all investigated aryl phosphates showed ame inhibition.
TMC-BDP worked as efciently as BDP in the gas phase,
whereas BEP was a less efcient H and OH scavenger
in PC/ABSPTFE.
Combining the BDP and TMC-BDP with PC/ABSPTFE leads
to the best UL 94 results and high LOI value, whereas the
blend PC/ABSPTFE + BEP shows no improvement of the
ammability results compared to non-ame-retarded
material.
All ame retardants worked as plasticizers. With
respect to glass transition temperatures, PC/ABSPTFE + TMC-BDP, with respect to HDT PC/ABSPTFE + BDP and
PC/ABSPTFE + TMC-BDP gave the best results among all
ame-retarded blends. BPD, TMC-BDP and BEP increase
slightly the mechanical modules, but decreased the impact
strength of PC/ABSPTFE to some extent. The blend with BEP
became extremely brittle due to a signicant degradation
in molecular weight during processing, when the phosphoric acid left in the synthesized BEP react with PC.
Overall, the comprehensive comparison of the following
ame-retarded
blends
PC/ABSPTFE + BDP,
PC/ABSPTFE + TMC-BDP and PC/ABSPTFE + BEP concludes that within
the class of aryl phosphate it is not easy to compete with
the ame retardancy performance of BDP in the PC/ABSPTFE
blend. However, we succeeded in proposing one more
ame retardant for PC/ABSPTFE that worked as well as
BDP. TMC-BDP showed similar performance in thermogravimerty and in cone calorimeter as BDP in PC/ABSPTFE.
Furthermore, the blend PC/ABSPTFE + TMC-BDP may even
be slightly better than PC/ABSPTFE + BDP with respect to
mechanical properties and glass transition temperatures.

Acknowledgements
The authors thank Bayer MaterialScience AG, Germany,
in particular Dr. V. Taschner, Dr. M. Jung, Dr. T. Eckel, and
Dr. D. Wittmann for providing the PC/ABSPTFE master batch
and BDP as well as for nancial support. Special thanks go
to H. Bahr, D. Neubert, F. Kempel for supporting us within
the cone calorimeter, DSC and rheological measurements,
respectively.
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