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Articulo 6 PDF
Articulo 6 PDF
Polymer
journal homepage: www.elsevier.com/locate/polymer
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.
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 index detector, and a PLgel Mixed D column with polystyrene gel
result, PDMS itself is not suitable for using as a flame retardant for particles of 5 mm in diameter as a stationary phase. The linear range
polymers. Other silicon-containing organic compounds could be of molecular weights for the PLgel Mixed D column in measure-
used as effective flame retardants, but they are relatively expensive. ment is 200e400,000 g/mol. The elution was performed using THF
The other candidates are inorganic silicon-containing compounds. with a flow rate of 1.0 mL min1 at 40 C. Mono-dispersed styrene
One example is silica nanoparticle, which has been reported to be samples were used as standards for molecular weight calibration.
able to depress the heat release rate and mass loss rate of polymer Differential scanning calorimetric (DSC) thermograms were recor-
matrix [18e20]. Nevertheless, the total amounts of heat release and ded with a TA-Q100 DSC instrument under a nitrogen flow in
mass loss of polymers do not change with the addition of silica 40 mL min1. Thermal stability of samples was measured with a
nanoparticles. Some papers have reported that silica nanoparticles thermogravimetric analyzer (TGA, Thermal Analysis TGA-Q500) at
are not effective agents as flame retardants for polymers [21,22]. a heating rate of 10 C min1. Scanning electron micrographs were
The reason is that silica nanoparticles are as huge as not being able recorded with a scanning electron microscopy (SEM) instrument of
to move in the polymer matrix to perform the above-mentioned Hitachi SEM S-4800. Atomic force microscopic (AFM) images were
mechanism of flame retardation. On the other hand, silica formed recorded with a JPK Instruments AG multimode NanoWizard
from in situ solegel reaction has showed a certain effect on the (Germany) equipped with a NanoWizard scanner and operated in
flame retardation of polymers [15,23,24], as in the cases the silica air. Limited oxygen index (LOI) values were measured on a Stanton
domain sizes are as small as being able to move toward to the Redcraft flame meter. 0.5 g samples in powder were used. The
polymer matrix surface to serve as the protective layer for the percentage in the O2eN2 mixture, deemed sufficient to sustain the
polymer matrix [15]. flame was taken as the LOI.
Basing on the flame retardation mechanism of silicon-containing
compounds, in this work branched and benzoxazine-containing 2.3. Preparation of benzoxazine-containing triethoxysilane
polysiloxanes (PBz-PSOs) have been prepared from polymerization compound Bz-TES
of a benzoxazine-containing trialkoxysilane compound (Bz-TES) and
diphenylsilanediol. The molecular design concepts of PBz-PSOs for Naphthol (12.6 g, 88 mmol), paraformaldehyde (3.5 g,
using as high performance flame retardants are: 176 mmol), and aminopropyltriethoxysilane (19.4 g, 88 mmol)
were dissolved in 400 mL of chloroform. The solution was charged
(a) PBz-PSOs are reactive-type flame retardants as they possess into a 1 L round-bottom flask and reacted at 85 C for 24 h. After
thermally-reactive benzoxazine groups; being cool to room temperature, the solvent was removed with a
(b) the benzoxazine groups in the structures favor char formation rotary evaporator. The residual was collected and dried under
of PBz-PSOs under thermal degradation [25]; vacuum at 40 C to give the solid product of Bz-TES with a yield of
(c) the silicon-containing groups of PBz-PSOs contribute to form about 93%. No further purification is needed. C21H31NO4Si: Calcd.: C
protective silica layers for polymer matrix under flame [10]; 64.62, H 7.95, N 3.59; Found: C 64.59, H 7.93, N 3.52.
(d) polymerization of silanediol and trialkoxysilane results in a
highly branched structure of PBz-PSOs, as branched poly- 2.4. Preparation of benzoxazine-containing branched polysiloxane
diphenylsiloxane chains have been reported to show higher PBz-PSO
flame retardant efficiency compared to the linear analog [26].
Bz-TES and barium hydroxide monohydrate (0.1 mol% of Bz-TES
With the multiple concepts of molecular design, the obtained PBz- and diphenylsilanediol) were dissolved in MEK, and the solution
PSOs materials show high limited oxygen index (LOI) values above 45, was charged into a round-bottom flask. The mixture was heated to
indicating their application potential as flame retardants for polymers. 100 C. Diphenylsilanediol was added slowly under nitrogen
Addition of 5 wt% of PBz-PSO to a conventional polybenzoxazine resin purging. After completing addition of diphenylsilanediol, the re-
simultaneously improves its flame retardancy to the UL 94-V0 grade action mixture was kept at 100 C for 10 h. The cool solution was
(3.2 mm), increases its Tg from 145 C to 205 C, and enhances its filtered with a Telflon filter with pore sizes of about 0.45 mm to
thermal stability. PBz-PSOs are not only halogen-free and remove BHM. The polymer was obtained from precipitation from
phosphorus-free flame retardants but also property enhancement methanol, and purified with the solution-precipitation method
agents for preparation of high performance polymeric materials. twice. Three PBz-PSO samples have been obtained with different
feeding ratios (2/2, 2/3, and 2/4) of Bz-TES and diphenylsilanediol.
2. Experimental 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
2.1. Materials amounts of Bz-TES and diphenylsilanediol, respectively.
Naphthol, aminopropyltriethoxysilane, diphenylsilanediol, and 2.5. Preparation of crosslinked PBz-PSO samples (CR-PBz-PSO)
barium hydroxide monohydrate were purchased from Aldrich
Chemical Co. and used as received. Paraformaldehyde was received Preparation of crosslinked PBz-PSO was carried out with the
from Tedia Co. Reagent grade solvents have been used as received. thermally-induced ring-opening polymerization of the benzox-
azine groups of PBz-PSO. The sample was thermally cured at 100 C
2.2. Characterization 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.
Fourier-transform infrared (FTIR) spectra were measured with a
Perkin Elmer Spectrum One FTIR spectroscopy. 1H and 29Si nuclear 3. Results and discussion
magnetic resonance (NMR) spectra were recorded with a Brüker
MSL-300 (300 MHz) NMR spectrometer and a Brüker 500 MHz 3.1. Benzoxazine-containing triethoxysilane compound (Bz-TES)
NMR spectrometer, respectively. The molecular weights of poly-
mers were measured with a gel permeation chromatography (GPC) Benzoxazine-based materials usually show high char yields in
composed of a LAB-Alliance Series III pump, an RI 2000 refractive thermal degradation, so they could be suitable agents to exhibit
C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951 2947
synergistic effect of flame retardation with the silicon-based flame two peaks have same peak areas. The protons of the ethoxy groups
retardants. In this work, the benzoxazine-containing triethox- result in the resonance peaks at d ¼ 1.28 ppm (eOCH2CH3) and
ysilane compound Bz-TES has been prepared as a precursor for d ¼ 3.87 ppm (eOCH2CH3). The resonance peaks of the protons of
preparation of highly efficient flame retardants. As shown in Scheme propylene group appear at d ¼ 0.74 ppm, d ¼ 1.78 ppm, and
1, Bz-TES has been obtained with aminopropyltriethoxysilane, d ¼ 2.84 ppm. The aromatic protons result in the resonance peaks
paraformaldehyde, and naphthol as precursors through the con- at d ¼ 7.03e7.82 ppm. Moreover, no resonance peaks appear in the
ventional method for preparation of benzoxazine compounds [25]. chemical shift region of about d ¼ 3.0e3.5 ppm, indicating the
After the reaction, Bz-TES in high purity could be obtained directly ring-opening reaction of the benzoxazine rings of Bz-TES did not
from removal of the solvent from the reaction solution without occur in the preparation process. On the other hand, the peak area
further purification. ratio of SieOCH2CH3 peaks over PheOeCH2e peaks is about 2.8,
The chemical structure of Bz-TES has been characterized with which is a little smaller than the theoretical value of 3.0. This result
FTIR and NMR. The results are shown in Fig. 1. In the FTIR spectrum indicates that about 6% of eSieOCH2CH3 groups of Bz-TES might
of Bz-TES, the absorption peaks of PheOeC at 1050 cm1 (sym- hydrolyze into SieOH groups. This result could be further charac-
metric stretching) and 1230 cm1 (asymmetric stretching) char- terized with the 29Si NMR spectrum of Bz-TES. As shown in Fig. 1-c,
acterize the benzoxazine ring structure of Bz-TES. The absorption Bz-TES shows two resonance peaks at d ¼ 45.2 ppm and
of the CeN group of benzoxazine ring overlaps with the absorption d ¼ 52.9 ppm corresponding to eSi(OEt)3 and eSi(OEt)2(OH),
of ethoxysilane group at about 1090 cm1. The triethoxysilane respectively. As a similar result has been observed with the NMR
group has been characterized with the absorption of SieOeC at spectra of the used aminopropyltriethoxysilane compound, the Sie
1080 cm1 and the absorption of eCH3 group at 2800e3000 cm1. OH groups in Bz-TES might be from the APTES precursor rather
The peaks at 1390, 1505, and 1610 cm1 associate to the absorption than from the hydrolysis reaction in the preparation reaction
of naphthalene group. Fig. 1-b shows the 1H NMR spectrum of Bz- process. Nevertheless, the small extent of SieOH groups should not
TES which provides further support to its chemical structure. The affect the further polymerization of Bz-TES with diphenylsilane-
typical resonance peaks of benzoxazine ring appear at diol. Fig. 1-d shows the DSC thermogram of Bz-TES under a heating
d ¼ 4.37 ppm (PheOeCH2e) and d ¼ 4.98 ppm (NeCH2eO). These 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.
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 3.3. Thermally crosslinked PBz-PSO samples (CR-PBz-PSO)
thermograms the PBz-PSO samples exhibit exothermic peaks at
about 130 C. The exothermic behavior has been attributed to the As PBz-PSO samples possess benzoxazine groups, PBz-PSOs are
ring-opening polymerization of benzoxazine groups. It is note- capable of performing crosslinking reaction to result in thermally-
worthy that the polymerization temperature of the benzoxazine crosslinked PBz-PSO samples (CR-PBz-PSO). As shown in Fig. 3,
groups of PBz-PSO is much lower than that of the benzoxazine PBz-PSO is transparent and brown (in the web version), and be-
group of Bz-TES. The relatively low reaction temperature of the comes dark brown after thermally-crosslinking reaction. The TGA
benzoxazine group of PBz-PSO could be due to the catalytic effect thermograms of the PBz-PSO samples before and after crosslinking
of the acidic silanol groups. The relatively low polymerization are shown in Fig. 4. For the uncrosslinked samples, the weight loss
temperature of PBz-PSO is favorable for their applications as at about 150 Ce200 C might arise from the condensation dehy-
flame retardants for thermosetting resins. After thermal treat- dration reaction between the residual SieOH groups. The weight
ment, the cross-linked PBz-PSO samples do not show exothermic loss at about 250 C has been attributed to the degradation of the
peaks in their DSC thermograms. This result also supports to that residual ethoxy groups. The extent of ethoxy groups decreases with
the exothermic behaviors of PBz-PSO samples result from their increasing in the diphenylsilanediol amounts in the feeding com-
benzoxazine polymerization. positions of polymerization. As a result, PBz-PSO-24 shows the
C.-Y. Hsieh et al. / Polymer 54 (2013) 2945e2951 2949
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 PSO-24 is enough for conventional polybenzoxazine resins to
result, PBz-PSO is not only a flame retardant but also an effective simultaneously improve its flame retardancy to pass the UL 94-V0
modifier for improvements of the property and performance of the test (3.2 mm), increase its Tg from 145 C to 205 C, and thermal
thermosetting resins. In a preliminary test, about 4.8 wt% of PBz- stability. Moreover, PBz-PSO-24 has also been used as a flame
retardant for some other polymers, as the results shown in Table 2.
Table 1
The molecular weight data of PBz-PSO samples and the thermal stability and flame
Further studies on the compatibility of the PBz-PSO flame
retardant property of cross-linked PBz-PSO samples.
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