Polymer 54 (2013) 2945e2951

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Benzoxazine-containing branched polysiloxanes: Highly efficient reactive-type

flame retardants and property enhancement agents for polymers
Chia-Yun Hsieh a, Wen-Chiung Su b, Chuan-Shao Wu c, Liang-Kai Lin d, Keh-Ying Hsu a, Ying-Ling Liu d, *
a
Department of Chemical Engineering and R&D Center for Membrane Technology, Chung Yuan Christian University, Chungli, Taoyuan 32023, Taiwan
b
Chemistry Division, Chung San Institute of Science and Technology, Lungtan, Taoyuan 32517, Taiwan
c
Department of Materials and Fiber and Graduate School of Materials Applied Technology, Taoyuan Institute of Innovation Technology, Chungli, Taoyuan 32091, Taiwan
d
Department of Chemical Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: The molecular design concept of silicon-nitrogen synergistic effect for highly-efficient flame retardants
Received 4 February 2013 has been demonstrated in the preparation of reactive type flame retardants which exhibits high flame
Received in revised form retardation efficiency and property enhancement ability for developments of high performance poly-
19 March 2013
mers. In the synthetic route, a benzoxazine-containing triethoxysilane compound is obtained and used as
Accepted 27 March 2013
Available online 6 April 2013
a monomer together with diphenylsilanediol to result in branched benzoxazine-containing polysiloxanes
(PBz-PSO) through a 3 þ 2 condensation polymerization reaction. The chemical structures and properties
of Bz-TES and PBz-PSO compounds have been characterized with Fourier transform infrared spectros-
Keywords:
Flame retardant
copy, nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. PBz-PSO samples
Halogen free are reactive polymers as they possess thermally-reactive benzoxazine groups. Thermally-crosslinking the
Polysiloxane PBz-PSO samples results in silicon-containing polymers which show high thermal stability and high
flame retardancy (limited oxygen index > 45). Addition of 5 wt% PBz-PSO to a conventional benzoxazine
resin could simultaneously improve its flame retardancy (passing the UL 94-V0 test) and increase its
glass transition temperature from 145  C to 205  C. PBz-PSO samples are highly-efficient reactive-type
flame retardants for preparation of halogen-free and phosphorus-free polymers.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction halogen-free and phosphorus-free flame retardants for polymeric

The developments of high performance halogen-free polymeric
materials for electronics, electrical, aerospace, and transportation
continue demanding high performance flame retardants.
Phosphorus-containing compounds and polymers have been
extensively studied to meet the requirements [1e4]. Nevertheless,
the phosphorus-containing flame retardants usually suffer from
hydrolysis, relatively poor thermal stability, and limited flame
retardation efficiency. Some synergistic systems basing on phos-
phorous flame retardants and other agents, such as nitrogen-
containing [5e7] and silicon-containing [8e12] materials, have
been reported to improve the flame-retardation efficiency, so as to
partly compensate the drawbacks of the phosphorus-containing
flame retardants. On the other hand, the impact of phosphorus to
the environments and human healthy draws certain concerns. The
environmental protection issue raises the needs of environmental
friendly polymeric materials and indicates the trends towards
* Corresponding author. Tel.: þ886 3 5711450; fax: þ886 3 5715408.
E-mail address: liuyl@mx.nthu.edu.tw (Y.-L. Liu).
materials [13e17].
Silicon-containing compounds are potential candidates of flame
retardants for high performance polymers. The flame retardation
mechanism of silicon-containing compounds has been illustrated
as (a) silicon moving toward matrix surface under heat (basing on
the low surface energy of silicon element) and (b) formation of
silica layer on the matrix surface [10]. The thermally-stable silica
serves as a protection and barrier layer for the polymer matrix, to
result in the reduction of (a) heat and oxygen gas transferring to the
polymer matrix, (b) thermal degradation rate and extent of the
polymer matrix, and (c) amounts of combustible gases released
from the degradation of the polymer matrix to the gas phase. As a
result, the efficiency of the silicon-based flame retardant is highly
dependent on the kind of polymer matrix. That is, the silicon-based
flame retardant is more suitable for a polymer matrix which is
capable of formation of a high char yield under thermal degrada-
tion/pyrolysis process [8,9]. On the other hand, the most popular
silicon-containing material is polydimethylsiloxane (PDMS). PDMS
thermally degrades at relatively low temperatures through a
depolymerization process, in which silicon elements evolve as D3
or D4 cyclic compounds in the gaseous degradation products. None

0032-3861/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymer.2013.03.060
2946 C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951
or less silica forms from PDMS under thermal degradation [13]. As a
result, PDMS itself is not suitable for using as a flame retardant for
polymers. Other silicon-containing organic compounds could be
used as effective flame retardants, but they are relatively expensive.
The other candidates are inorganic silicon-containing compounds.
One example is silica nanoparticle, which has been reported to be
able to depress the heat release rate and mass loss rate of polymer
matrix [18e20]. Nevertheless, the total amounts of heat release and
mass loss of polymers do not change with the addition of silica
nanoparticles. Some papers have reported that silica nanoparticles
are not effective agents as flame retardants for polymers [21,22].
The reason is that silica nanoparticles are as huge as not being able
to move in the polymer matrix to perform the above-mentioned
mechanism of flame retardation. On the other hand, silica formed
from in situ solegel reaction has showed a certain effect on the
flame retardation of polymers [15,23,24], as in the cases the silica
domain sizes are as small as being able to move toward to the
polymer matrix surface to serve as the protective layer for the
polymer matrix [15].
Basing on the flame retardation mechanism of silicon-containing
compounds, in this work branched and benzoxazine-containing
polysiloxanes (PBz-PSOs) have been prepared from polymerization
of a benzoxazine-containing trialkoxysilane compound (Bz-TES) and
diphenylsilanediol. The molecular design concepts of PBz-PSOs for
using as high performance flame retardants are:
(a) PBz-PSOs are reactive-type flame retardants as they possess
thermally-reactive benzoxazine groups;
(b) the benzoxazine groups in the structures favor char formation
of PBz-PSOs under thermal degradation [25];
(c) the silicon-containing groups of PBz-PSOs contribute to form
protective silica layers for polymer matrix under flame [10];
(d) polymerization of silanediol and trialkoxysilane results in a
highly branched structure of PBz-PSOs, as branched poly-
diphenylsiloxane chains have been reported to show higher
flame retardant efficiency compared to the linear analog [26].
With the multiple concepts of molecular design, the obtained PBz-
PSOs materials show high limited oxygen index (LOI) values above 45,
indicating their application potential as flame retardants for polymers.
Addition of 5 wt% of PBz-PSO to a conventional polybenzoxazine resin
simultaneously improves its flame retardancy to the UL 94-V0 grade
(3.2 mm), increases its Tg from 145  C to 205  C, and enhances its
thermal stability. PBz-PSOs are not only halogen-free and
phosphorus-free flame retardants but also property enhancement
agents for preparation of high performance polymeric materials.
2. Experimental
2.1. Materials
Naphthol, aminopropyltriethoxysilane, diphenylsilanediol, and
barium hydroxide monohydrate were purchased from Aldrich
Chemical Co. and used as received. Paraformaldehyde was received
from Tedia Co. Reagent grade solvents have been used as received.
2.2. Characterization
Fourier-transform infrared (FTIR) spectra were measured with a
Perkin Elmer Spectrum One FTIR spectroscopy. 1H and 29Si nuclear
magnetic resonance (NMR) spectra were recorded with a Brüker
MSL-300 (300 MHz) NMR spectrometer and a Brüker 500 MHz
NMR spectrometer, respectively. The molecular weights of poly-
mers were measured with a gel permeation chromatography (GPC)
composed of a LAB-Alliance Series III pump, an RI 2000 refractive
index detector, and a PLgel Mixed D column with polystyrene gel
particles of 5 mm in diameter as a stationary phase. The linear range
of molecular weights for the PLgel Mixed D column in measure-
ment is 200e400,000 g/mol. The elution was performed using THF
with a flow rate of 1.0 mL min1 at 40  C. Mono-dispersed styrene
samples were used as standards for molecular weight calibration.
Differential scanning calorimetric (DSC) thermograms were recor-
ded with a TA-Q100 DSC instrument under a nitrogen flow in
40 mL min1. Thermal stability of samples was measured with a
thermogravimetric analyzer (TGA, Thermal Analysis TGA-Q500) at
a heating rate of 10  C min1. Scanning electron micrographs were
recorded with a scanning electron microscopy (SEM) instrument of
Hitachi SEM S-4800. Atomic force microscopic (AFM) images were
recorded with a JPK Instruments AG multimode NanoWizard
(Germany) equipped with a NanoWizard scanner and operated in
air. Limited oxygen index (LOI) values were measured on a Stanton
Redcraft flame meter. 0.5 g samples in powder were used. The
percentage in the O2eN2 mixture, deemed sufficient to sustain the
flame was taken as the LOI.
2.3. Preparation of benzoxazine-containing triethoxysilane
compound Bz-TES
Naphthol (12.6 g, 88 mmol), paraformaldehyde (3.5 g,
176 mmol), and aminopropyltriethoxysilane (19.4 g, 88 mmol)
were dissolved in 400 mL of chloroform. The solution was charged
into a 1 L round-bottom flask and reacted at 85  C for 24 h. After
being cool to room temperature, the solvent was removed with a
rotary evaporator. The residual was collected and dried under
vacuum at 40  C to give the solid product of Bz-TES with a yield of
about 93%. No further purification is needed. C21H31NO4Si: Calcd.: C
64.62, H 7.95, N 3.59; Found: C 64.59, H 7.93, N 3.52.
2.4. Preparation of benzoxazine-containing branched polysiloxane
PBz-PSO
Bz-TES and barium hydroxide monohydrate (0.1 mol% of Bz-TES
and diphenylsilanediol) were dissolved in MEK, and the solution
was charged into a round-bottom flask. The mixture was heated to
100  C. Diphenylsilanediol was added slowly under nitrogen
purging. After completing addition of diphenylsilanediol, the re-
action mixture was kept at 100  C for 10 h. The cool solution was
filtered with a Telflon filter with pore sizes of about 0.45 mm to
remove BHM. The polymer was obtained from precipitation from
methanol, and purified with the solution-precipitation method
twice. Three PBz-PSO samples have been obtained with different
feeding ratios (2/2, 2/3, and 2/4) of Bz-TES and diphenylsilanediol.
The samples were obtained with yields of about 85 wt%. They are
named as PBz-PSO-XY, in which X and Y denote the relative molar
amounts of Bz-TES and diphenylsilanediol, respectively.
2.5. Preparation of crosslinked PBz-PSO samples (CR-PBz-PSO)
Preparation of crosslinked PBz-PSO was carried out with the
thermally-induced ring-opening polymerization of the benzox-
azine groups of PBz-PSO. The sample was thermally cured at 100  C
for 1 h, 220  C for 1 h, and 250  C for another 1 h. Three CR-PBz-PSO
samples were obtained with the same manner.
3. Results and discussion
3.1. Benzoxazine-containing triethoxysilane compound (Bz-TES)
Benzoxazine-based materials usually show high char yields in
thermal degradation, so they could be suitable agents to exhibit
 C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951
synergistic effect of flame retardation with the silicon-based flame
retardants. In this work, the benzoxazine-containing triethox-
ysilane compound Bz-TES has been prepared as a precursor for
preparation of highly efficient flame retardants. As shown in Scheme
1, Bz-TES has been obtained with aminopropyltriethoxysilane,
paraformaldehyde, and naphthol as precursors through the con-
ventional method for preparation of benzoxazine compounds [25].
After the reaction, Bz-TES in high purity could be obtained directly
from removal of the solvent from the reaction solution without
further purification.
The chemical structure of Bz-TES has been characterized with
FTIR and NMR. The results are shown in Fig. 1. In the FTIR spectrum
of Bz-TES, the absorption peaks of PheOeC at 1050 cm1 (sym-
metric stretching) and 1230 cm1 (asymmetric stretching) char-
acterize the benzoxazine ring structure of Bz-TES. The absorption
of the CeN group of benzoxazine ring overlaps with the absorption
of ethoxysilane group at about 1090 cm1. The triethoxysilane
group has been characterized with the absorption of SieOeC at
1080 cm1 and the absorption of eCH3 group at 2800e3000 cm1.
The peaks at 1390, 1505, and 1610 cm1 associate to the absorption
of naphthalene group. Fig. 1-b shows the 1H NMR spectrum of Bz-
TES which provides further support to its chemical structure. The
typical resonance peaks of benzoxazine ring appear at
d ¼ 4.37 ppm (PheOeCH2e) and d ¼ 4.98 ppm (NeCH2eO). These
Scheme 1. Synthesis of benzoxazine-containing triethoxysilane compound (Bz-TES)
and benzoxazine-containing branched polysiloxanes (PBz-PSO).
2947
two peaks have same peak areas. The protons of the ethoxy groups
result in the resonance peaks at d ¼ 1.28 ppm (eOCH2CH3) and
d ¼ 3.87 ppm (eOCH2CH3). The resonance peaks of the protons of
propylene group appear at d ¼ 0.74 ppm, d ¼ 1.78 ppm, and
d ¼ 2.84 ppm. The aromatic protons result in the resonance peaks
at d ¼ 7.03e7.82 ppm. Moreover, no resonance peaks appear in the
chemical shift region of about d ¼ 3.0e3.5 ppm, indicating the
ring-opening reaction of the benzoxazine rings of Bz-TES did not
occur in the preparation process. On the other hand, the peak area
ratio of SieOCH2CH3 peaks over PheOeCH2e peaks is about 2.8,
which is a little smaller than the theoretical value of 3.0. This result
indicates that about 6% of eSieOCH2CH3 groups of Bz-TES might
hydrolyze into SieOH groups. This result could be further charac-
terized with the 29Si NMR spectrum of Bz-TES. As shown in Fig. 1-c,
Bz-TES shows two resonance peaks at d ¼ 45.2 ppm and
d ¼ 52.9 ppm corresponding to eSi(OEt)3 and eSi(OEt)2(OH),
respectively. As a similar result has been observed with the NMR
spectra of the used aminopropyltriethoxysilane compound, the Sie
OH groups in Bz-TES might be from the APTES precursor rather
than from the hydrolysis reaction in the preparation reaction
process. Nevertheless, the small extent of SieOH groups should not
affect the further polymerization of Bz-TES with diphenylsilane-
diol. Fig. 1-d shows the DSC thermogram of Bz-TES under a heating
scan at a heating rate of 10  C min1. Bz-TES exhibits an exothermic
peak which results from the ring-opening addition reaction of the
benzoxazine groups. The exothermic peak demonstrates the
presence of benzoxazine group in Bz-TES compound.
3.2. Benzoxazine-containing branched polysiloxanes (PBz-PSO)
Bz-TES has been utilized as a monomer to polymerize with
diphenylsilanediol for preparation of benzoxazine-containing pol-
ysiloxanes PBz-PSO. The reaction route is illustrated in Scheme 1.
The polymerization has been carried out through a nonhydrolytic
solegel reaction between Bz-TES and diphenylsilanediol using
barium hydroxide monohydrate as a reaction promoter [27]. Bz-TES
is a trifunctional monomer and diphenylsilanediol is a difunctional
monomer. As a result, this is a 3 þ 2 condensation polymerization,
which might result in branched polysiloxane products. Fig. 2 shows
the characterization results of the obtained PBz-PSO samples. In the
FTIR spectrum, the absorptions of the Si-Ph and phenyl groups of
diphenylsilanediol units in PBz-PSO appear at 1240 and 1602 cm1,
respectively. The formation of SieOeSi linkages results in a broad
absorption at about 1150 cm1. The absorptions of the benzoxazine
groups still could be found at 1050 and 1230 cm1. On the other
hand, free diphenylsilanediol shows a resonance peak at
d ¼ 28 ppm in the 29Si NMR analysis. This peak does not appear in
the 29Si NMR spectrum of PBz-PSO. As a result, there is not free
diphenylsilanediol compound retained in the PBz-PSO sample. In
the 29Si NMR spectrum of PBz-PSO-24, the two groups of resonance
peaks at d ¼ 42 to 46 ppm and d ¼ 54 to 67 ppm correspond
to the silicon atoms of diphenylsilanediol and triethoxysilane de-
rivatives, respectively. The peak at about d ¼ 67 ppm corresponds
to the completely-condensed silicon (T3, eSie(OSi)3) formed from
the condensation reaction of the triethoxysilane groups. The peak
corresponding to T2 (eSi(OH)e(OSi)2) structure also appears at
d ¼ 58 ppm. It is noteworthy that the intensity of the peak
(d ¼ 54 ppm) corresponding to the T1 structure (eSi(OH)2e(OSi)) is
very small, indicating the high conversion of the condensation re-
action of the triethoxysilane groups.
The three PBz-PSO samples have similar number-averaged
molecular weights of about 5000e5350 g mol1 and different
polydispersity indexes (PDI). PBz-PSO-22 has a PDI value of 1.17.
The PDI values of PBz-PSO-23 and PBz-PSO-24 are 1.52 and 1.30,
respectively. PBz-PSO-23 has the highest PDI value as it was
2948 C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951

Fig. 1. Characterization of benzoxazine-containing triethoxysilane compound (Bz-TES) with (a) FTIR, (b) 1H NMR, (c) 29
Si NMR, and (d) DSC.

obtained with the monomers fed in equal equivalents. In the DSC
thermograms the PBz-PSO samples exhibit exothermic peaks at
about 130  C. The exothermic behavior has been attributed to the
ring-opening polymerization of benzoxazine groups. It is note-
worthy that the polymerization temperature of the benzoxazine
groups of PBz-PSO is much lower than that of the benzoxazine
group of Bz-TES. The relatively low reaction temperature of the
benzoxazine group of PBz-PSO could be due to the catalytic effect
of the acidic silanol groups. The relatively low polymerization
temperature of PBz-PSO is favorable for their applications as
flame retardants for thermosetting resins. After thermal treat-
ment, the cross-linked PBz-PSO samples do not show exothermic
peaks in their DSC thermograms. This result also supports to that
the exothermic behaviors of PBz-PSO samples result from their
benzoxazine polymerization.
3.3. Thermally crosslinked PBz-PSO samples (CR-PBz-PSO)
As PBz-PSO samples possess benzoxazine groups, PBz-PSOs are
capable of performing crosslinking reaction to result in thermally-
crosslinked PBz-PSO samples (CR-PBz-PSO). As shown in Fig. 3,
PBz-PSO is transparent and brown (in the web version), and be-
comes dark brown after thermally-crosslinking reaction. The TGA
thermograms of the PBz-PSO samples before and after crosslinking
are shown in Fig. 4. For the uncrosslinked samples, the weight loss
at about 150  Ce200  C might arise from the condensation dehy-
dration reaction between the residual SieOH groups. The weight
loss at about 250  C has been attributed to the degradation of the
residual ethoxy groups. The extent of ethoxy groups decreases with
increasing in the diphenylsilanediol amounts in the feeding com-
positions of polymerization. As a result, PBz-PSO-24 shows the
 C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951
Fig. 2. Characterization of benzoxazine-containing branched polysiloxanes (PBz-PSO-
24) with (a) FTIR and (b) 29Si NMR.
minimum extent of weight loss at this stage of degradation, as it has
relatively small amount of Bz-TES in the polymerization composi-
tion. All the three uncrosslinked samples exhibit char yields of
about 20 wt%. On the other hand, the crosslinked samples show
very different degradation patterns in TGA analysis. It is noteworthy
that CR-PBz-PSO-22 exhibits the highest thermal stability and char
yield among the three samples. This result could be understood
with that PBz-PSO-22 possesses the highest fraction of benzoxazine
and triethoxysilane groups, to result in that CR-PBz-PSO-22 has the
highest crosslinking density among the three crosslinked samples.
Polybenzoxazine structure favors the formation of char in thermal
degradation. Consequently, the high char yield of CR-PBz-PSO-22
has been attributed to its high benzoxazine content. As it can be
Fig. 3. Polymerization of benzoxazine-containing branched polysiloxanes (PBz-PSO)
through the ring-opening addition reaction of benzoxazine groups. The pictures of
PBz-PSO sample before and after polymerization are included.
2949
Fig. 4. TGA thermograms of PBz-PSO polymers and their corresponding crosslinked
samples (in nitrogen atmosphere at a heating rate of 10  C min1).
seen in Fig. 4, at 800  C the char yield of CR-PBz-PSO-22 is as high as
55 wt%. High char yield indicates that less flammable degradation
products have been revealed to the gaseous phase in the thermal
degradation of the sample. Less flammable gaseous products in
degradation could be correlated to higher flame resistance. This
will be discussed later.
Fig. 5 shows the SEM and AFM micrographs of CR-PBz-PSO
samples for morphological studies. Silica-like aggregates in the
sizes of about 20e40 nm appear in the cross-sectional SEM images.
The sizes of the aggregates increase with the decreases in the
contents of diphenylsilanediol of the samples. The more Bz-TES is in
the polymerization composition, the more branched SieOeSi
linkages form in the structures of PBz-PSOs. As PBz-PSO-22 has the
highest fraction of Bz-TES in the preparation composition, more
silica-like structures form in CR-PBz-PSO-22 so as to favor the
formation of organiceinorganic microphase separation in the
sample. In the surface AFM micrographs, the relatively bright re-
gion corresponds to the silicon-rich structure. CR-PBz-PSO-24
shows the most obvious bright patterns in its AFM micrograph,
indicates more silicon-rich structures form on the surface of CR-
PBz-PSO-24. In the thermal curing process, the relatively-low sur-
face energy of silicon elements drives them moving toward the
sample surfaces. As PBz-PSO-24 possesses the smallest amount of
benzoxazine group and the resulting CR-PBz-PSO-24 has a rela-
tively low crosslinking density, the motion of silicon toward the CR-
PBz-PSO-24 sample surface is relatively easy. Formation of silica-
like structures on the CR-PBz-PSO-24 sample surface also in-
creases its thermal stability. As it can be seen in the TGA thermo-
grams, the thermal stability of CR-PBz-PSO-24 is much higher than
that of CR-PBz-PSO-23.
3.4. Reactive flame retardants for polymers
The flame retardancy of the CR-PBz-PSO samples has been
evaluated with their LOI values. The results have been collected in
Table 1. All three samples show LOI values above 45 (the upper limit
of the used measurement). The high LOI values demonstrate high
flame retardancy of the CR-PBz-SO samples, and the achievement
of the concept of molecular design on the nitrogen-silicon syner-
gistic effect of flame retardation in this work.
The above results indicate that the prepared PBz-PSO samples
are suitable reactive type flame retardants for polymers. For ther-
mosetting polymers, PBz-PSO could be directly added to the resin
varnishes and in situ be crosslinked in the curing process of the
resins. The products could be an interpenetrating network of the
2950 C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951

Fig. 5. SEM (left) and AFM (right) micrographs of the crosslinked CR-PBz-PSO samples.

thermosetting matrix and the CR-PBz-PSO flame retardant. As a
result, PBz-PSO is not only a flame retardant but also an effective
modifier for improvements of the property and performance of the
thermosetting resins. In a preliminary test, about 4.8 wt% of PBz-
Table 1
The molecular weight data of PBz-PSO samples and the thermal stability and flame
retardant property of cross-linked PBz-PSO samples.
PSO-24 is enough for conventional polybenzoxazine resins to
simultaneously improve its flame retardancy to pass the UL 94-V0
test (3.2 mm), increase its Tg from 145  C to 205  C, and thermal
stability. Moreover, PBz-PSO-24 has also been used as a flame
retardant for some other polymers, as the results shown in Table 2.
Further studies on the compatibility of the PBz-PSO flame

Sample GPC data Thermal properties from TGAa LOIa Table 2

b
Flame retardation efficiency of PBz-PSO-24 for some polymers.
Mn PDI Td10 Char yield
(g mol1) ( C) at 800  C (wt%) Matrix polymers Required amounts of
PBz-PSO-22 5020 1.17 410 55 >45c PBz-PSO-24 for passing
PBz-PSO-23 5120 1.52 350 50 >45 UL 94-V0 test (3.2 mm) (wt%)
PBz-PSO-24 5350 1.30 385 44 >45 Bisphenol-A/aniline benzoxazine 4.8
a Bisphenol-A epoxy/dicyandiamide resin 6.5
TGA and LOI data obtained with the crosslinked (CR-PBz-PSO) samples.
b Poly(2,6-dimethylphenyl oxide) 3.0
Temperatures at 10 wt% loss.
c Arylonitrile/butadiene/styrene copolymer 15
The LOI measurements have been carried out with an upper limit of LOI ¼ 45.
 C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951 2951

retardants and the polymer matrix and the thermal and mechanical References
properties of the obtained PBz-PSO-added polymers are under
studies. [1] Lu SY, Hamerton I. Prog Polym Sci 2002;27:1661.
[2] Liu YL. J Polym Sci Part A Polym Chem 2002;40:359.
[3] Bourbigot S, Duquesne S. J Mater Chem 2007;17:2283.
4. Conclusion [4] Chang HC, Lin HT, Lin CH. Polym Chem 2012;3:970.
[5] Hsieh JY, Wang CS. Polymer 2001;42:7617.
[6] Wu CS, Liu YL, Chiu YS. Polymer 2002;43:4277.
A series of benzoxazine-containing branched polysiloxanes have [7] Tai Q, Hu Y, Yuan RKK, Song L, Lu H. J Mater Chem 2011;21:6621.
been prepared using a benzoxazine-containing triethoxysilane and [8] Hsiue GH, Liu YL. J Appl Polym Sci 2000;78:1.
diphenylsilanediol as monomers. These products are suitably used [9] Liu YL, Chiu YC, Wu CS. J Appl Polym Sci 2003;87:404.
[10] Liu YL, Chou CI. Polym Degrad Stab 2005;90:515.
as reactive type flame retardants for polymers as they possess [11] Song ML, Huang YW, Cao K, Yang Y. Adv Mater Res 2012;534:304.
reactive benzoxazine groups in the side chains and show high LOI [12] Zhang K, Shen MM, Wu K, Liu HF. J Polym Res 2011;18:2061.
values above 45, which demonstrates the success of molecular [13] Liu YL, Lee SH. Macromol Rapid Commun 2004;25:1392.
[14] Huang H, Tian M, Liu L, He Z, Chen Z, Zhang L. J Appl Polym Sci 2006;99:3203.
design on the nitrogen-silicon synergistic effect of flame retarda- [15] Zhang S, Gu A, Liang G, Hu J, Yuan L, Chen X. J Mater Chem 2011;21:6584.
tion in this work. PBz-PSO is also an effective property modifier for [16] Mosurkal R, Kirby R, Muller WS, Soares JW, Kumar J. Green Chem 2011;13:659.
thermosetting polymers as it could form IPN structures with the [17] Ravichandran S, Nagarajan S, Ku BC, Coughlin C, Emrick T, Kumar J, et al.
Green Chem 2012;14:819.
thermosets matrix. In conclusion, the PBz-PSO products are novel [18] Kashiwagi T, Morgan AB, Antonucci JM, Van Landingham MR, Harris RH,
highly-efficient flame retardants and property enhancing agents for Awad WH, et al. J Appl Polym Sci 2003;89:2072.
polymers. [19] Kashiwagi T, Gilman JW, Butler KM, Harris RH, Shields JR. Fire Mater 2000;24:277.
[20] Kashiwagi T, Shields JR, Harris RH, Davis RDR. J Appl Polym Sci 2003;87:1541.
[21] Yang F, Nelson GL. J Appl Polym Sci 2004;91:3844.
Acknowledgment [22] Liu YL, Hsu CY, Wei WL, Jeng RJ. Polymer 2003;44:5159.
[23] Chiang CL, Ma CCM, Wu DL, Kuan HC. J Polym Sci Part A Polym Chem 2003;41:905.
[24] Chiang CL, Ma CCM. J Polym Sci Part A Polym Chem 2003;41:1371.
Financial supports on this work from Chung San Institute of
[25] Liu YL, Chou CI. J Polym Sci Part A Polym Chem 2005;43:5267.
Science and Technology, Taiwan (Grant No. CSIST-0497-V210(101)) [26] Iji M, Serizawa S. Polym Adv Technol 1998;9:1.
is highly appreciated. [27] Yang SC, Kim JS, Jin JH, Kwak SY, Bae BS. J Appl Polym Sci 2011;122:2478.