Synthesis, characterization and curing behavior of methyl-tri(phenylethynyl)silane

Article abstract of DOI:10.1007/s11164-015-2307-8

Methyl-tri(phenylethynyl)silane ((ph-C≡C)₃-Si-CH₃) (MTPES) was synthesized with methyltrichlorosilane and phenylethylene by Grignard reaction. Its molecular structure was characterized by Fourier transform infrared spectroscopy, nucl

Full text of DOI:10.1007/s11164-015-2307-8

Res Chem Intermed
DOI 10.1007/s11164-015-2307-8
Synthesis, characterization and curing behavior
of methyl-tri(phenylethynyl)silane
Dexin Tan1 Xiaole Wu1 Yanli Wang2
•
•
•
Yuan Xu1 Honglong Xing1
•
Received: 5 July 2015 / Accepted: 28 September 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract Methyl-tri(phenylethynyl)silane ((ph-C:C)3-Si-CH3) (MTPES) was
synthesized with methyltrichlorosilane and phenylethylene by Grignard reaction. Its
molecular structure was characterized by Fourier transform infrared spectroscopy,
nuclear magnetic resonance (1H-NMR, 13C-NMR, and 29Si-NMR). Its curing
behavior was analyzed by non-isothermal differential scanning calorimetry and
rheometry, and the corresponding kinetic parameters and kinetic model were also
discussed by Kissinger, Ozawa, Flynn–Wall–Ozawa and Friedman methods. The
results showed that the melting point of MTPES was 130 °C and the processing
window was 200 °C. The activation energy Ea, pre-exponential factor lnA and the
reaction order n, m were 112.58 kJ/mol, 21.22 (s-1), 1.20 and 0.56, respectively.
The curing behavior of MTPES followed the autocatalytic kinetic model.
Keywords Methyl-tri(phenylethynyl)silane Á Grignard reaction Á Curing
behavior Á Differential scanning calorimetry Á Rheometry
Introduction
The silicon-containing arylacetylenic monomer has received intense interest. This
kind of arylacetylenic monomer can cure to form a crosslinked structure by thermal
self-polymerization with the advantage of a large processing window [1, 2]. In
addition, its polymers have the properties of high temperature resistance, high char
yield and high radiation resistance. All these properties support potential
&
Dexin Tan
tdxin@163.com
1
2
School of Chemical Engineering, Anhui University of Science and Technology,
Huainan 232001, China
School of Materials Science and Engineering, Anhui University of Science and Technology,
Huainan 232001, China
123

D. Tan et al.
applications in biomaterials, optoelectronics, wave-transmitting materials, semi-
conductor materials, ceramic precursors and so forth [3, 4].
Numerous examples with different substituents at the Si bond, such as hydrogen,
alkyl, phenyl or vinyl groups, have been reported [5–9]. Wrackmeyer et al. [8] divided
the preparation of various alkynylsilanes into two methods. One is that of sophisticated
reactions with rigorous reaction conditions and expensive raw materials (e.g.
ruthenium), which are mainly limited to laboratory preparation. The other is that of
conventional reactions of commercial chlorosilanes with alkynyllithium or ethynyl
magnesium reagents. In these cases, Grignard reactions are mild, and some silicon-
containing arylacetylenic monomers (e.g., methyldi(phenylethynyl)silane) are also
prepared by Grignard reactions and the yields are better than 75 % [10, 11].
As a kind of silicon-containing arylacetylene monmer, methyl-tri(phenylethynyl)-
silane (MTPES) was first reported using dianionic hexacoordinated siliconcomplexes,
sodium bis(benzene-1,2-diolato) methylsilicate and phenylacetylene as raw materials
by Grignard reagent or organolithium reagents, and the effects of different
organometallic reagents, reaction time and temperature on yield were discussed [12,
13]. Kim and Wrackmeyer prepared the MTPES with phenylacetylene and lithium
reagent, and made a basic structural analysis by nuclear magnetic resonanc (NMR) and
X-ray diffraction (XRD) [8, 14]. Zhou et al. also synthesized the MTPES with
butyllithium and phenylacetylene and further confirmed its molecule structure by high
resolution mass spectrometer (HRMS), Fourier transform infrared spectroscopy (FT-
IR), NMR and elemental analysis (EA). At the same time, the reaction activation
energy and reaction order were also obtained using Kissinger and Ozawa methods by
differential scanning calorimetry (DSC) curves [15, 16]. However, the synthetic route
with methyltrichlorosilane and phenylethylene, and the corresponding curing process
(curing schedule, curing kinetic model) are not reported.
In this study, we prepared MTPES using the relative inexpensive methyltrichlorosi-
lane and phenylethylene by Grignard reaction and the corresponding curing schedule
was obtained by DSC and was further verified by FT-IR and rheometry. The kinetic
parameters were obtained combined with Kissinger, Ozawa, Flynn–Wall–Ozawa and
Friedman methods, and the kinetic model was also established.
Experimental
Materials and methods
Phenylacetylene and methyltrichlorosilane was obtained from aike Reagent
Company, China. Magnesium ribbons (Chengdu KeLong Chemical Company)
were treated before being used. All chemicals and solvents were used according to
standard treatment procedures.
Preparation of methyl-tri(phenylethynyl)silane monomer
At first, magnesium Grignard reagent was prepared as follows: The magnesium
metal ribbon (1.68 g) was introduced into a 125-ml, three-necked round bottom
123

Synthesis, characterization and curing behavior of…
flask with a condenser, a dropping funnel, nitrogen gas and a stirrer. THF (20 ml)
was introduced into the flask, a small piece of iodine was added and then the
mixture was stirred to activate the reaction. A solution of 5 ml ethylbromide in THF
(25 ml) was added dropwise to the activated magnesium at room temperature over
the course of about 1 h. The resulting mixture continued to be refluxed over 3 h to
produce ethylmagnesium bromide.
Then a solution of 7.4 ml phenylacetylene in THF (25 ml) was added dropwise
in an ice-bath over the course of 1 h, and the reaction was secondly refluxed over
3 h to prepare the phenylethynylene Grignard reagent. The MTPES was prepared by
the following procedures: 2.6 ml methyl-trichlorosilane in THF (25 ml) was added
dropwise to the flask in an ice-bath over 1 h and refluxed over 3 h. The solution was
gradually added as 33 ml of 1 mol/l aqueous solution of hydrochloric acid after
cooling. Toluene (12.5 ml) was used to separate the oil phase, which was then
washed with distilled water until neutral, followed by drying to stand overnight. The
solvent was distilled off with vacuum distillation to eventually give an orange crude
product, and was further recrystallized in ethanol to cause repeated precipitation.
The precipitates were filtered off and branch shape crystals were obtained (5.08 g,
65.76 % yield) (Fig. 1a).
Fig. 1 Synthesis and structural information of MTPES (a synthetic route, b 1H-NMR, c 13C-NMR,
d
29Si-NMR)
123

D. Tan et al.
Characterization
FT-IR spectrum was carried out with Nicolet 380 FT-IR Spectrometer by potassium
1
bromide (KBr) pellets. H-NMR, 13C-NMR and 29Si-NMR spectra were traced on
an AVANCE AV-400 Super-conducting Fourier Digital NMR Spectrometer
(400 MHz for 1H-NMR, 100.61 MHz for 13C-NMR and 79.49 MHz for 29Si-
NMR). The chemical shifts were recorded relative to tetramethylsilane (d, 0.0 ppm)
1
for H-NMR, 29Si-NMR and CDCl3 (d, 77.7 ppm) for 13C-NMR. The DSC was
operated on a NETZSCH STA 449F3 instrument at the flow rate of 20 m/min
nitrogen atmosphere. Rheological behavior was traced by TA AR-G2 Rheometer at
3 °C/min and a shear rate of 0.01 s-1
.
Results and discussion
Structural analysis of MTPES
1H-NMR spectrum of MTPES is shown in Fig. 1b. The silicon methyl protons
resonates at 0.71 ppm and aromatic hydrogen resonates at 7.32–7.56. In a precise
NMR peak integration, the ratio of methyl protons (m, 3H, CH3–), aromatic
hydrogen (m, 6H, PhH-C:C) adjacent to ethynyl and other aromatic hydrogens (m,
9H, PhH) is 3:6:9.
The carbon spectrum of MTPES is described in Fig. 1c. The methyl bonded to
the silicon was 1.63 ppm (Si-CH3). The acetylenic carbons appear at 88 and
106 ppm, bonded to the silicon and phenyl unit. The phenyl carbons are
symmetrical and have resonances between 122.17 and 132.53 ppm. 29Si-NMR
spectrum of MTPES is presented in Fig. 1d. The signal peak assigned to the silicon
is observed at -64.22 ppm, while the road peak at about -110 ppm may be caused
1
by the silicon dioxide in the NMR tube. Based on the H-NMR, 13C-NMR, 29Si-
NMR spectra, the results are in agreement with the structure of MTPES [8, 15].
Curing behavior of MTPES
Curing schedule of MTPES
Figure 2 shows the DSC thermograms of MTPES at different heating rates. The
endothermal peak at 130 °C is the melting point, and the initial curing temperature
(Ti), peak temperature (Tp), final curing temperature (Tf) and curing time can be
derived, as in Table 1. With the increasing heating rate, the exothermic peak shifts
to a higher temperature and the curing time is shortened.
The processing properties of material are crucial to its application, and the
processing temperature is an important aspect of processing properties. In order to
get proper schedule parameters of MTPES, extrapolation method is often used [17].
Namely, there was a linear relationship between the temperature (T) and heating rate
(b), and the best processing temperature could be acquired when b = 0 °C/min.
123

Synthesis, characterization and curing behavior of…
7
6
25˚C/min
5
4
20˚C/min
15˚C/min
10˚C/min
3
5˚C/min
2
1
0
-1
100
150
200
250
300
350
400
450
T (˚C)
Fig. 2 A typical DSC curves of MTPES at different heating rates
Table 1 Curing parameters of MTPES at different heating rates
b (°C/min)
Ti
Tp
Tf
Curing time (min)
DH (kJ/mol)
5
307.4
314.6
320.4
327.7
331.9
337.0
356.0
366.0
375.1
381.3
366.2
385.4
406.7
413.8
424.5
11.76
7.08
5.75
4.31
3.70
178.29
131.83
281.16
240.36
232.85
10
15
20
25
According to the results shown in Fig. 3 and Table 2, the cure schedule of
MTPES was determined as follows: (302 °C, 1 h) ? (331 °C, 2 h) ? (356 °C, 1 h)
and the corresponding polymer (PMTPES) was also obtained by the curing process
mentioned above. The typical FT-IR spectra of MTPES and PMTPES are presented
in Fig. 4. The most notable change is that the PMTPES shows the complete absence
of 2168 cm-1 (C:C) and the peak of 1631–1440 cm-1 stretching becomes much
weaker (aromatic ring), indicating that the cure mechanism might be a radical
mechanism leading to a polyene network rather than trimerization of ethynyl group
leading to benzene rings, which is consistent with the literature reported [16, 18].
The viscosity–temperature curve of MTPES is shown in Fig. 5. As the
temperature increases, the viscosity keeps constant at 80 Pa s and then elevates
dramatically at 330 °C, corresponding to the gelation temperature of MTPES.
Combined with DSC curves and rheological curve, it was shown that the melting
point and gelation temperature of MTPES were 130 and 330 °C, respectively. This
was in agreement with the cure parameters mentioned above, and the 200 °C
processing window was able to ensure adequate flow behavior to impregnate other
materials for preparing functional composites.
123

D. Tan et al.
420
400
380
360
340
320
300
Ti
T
p
Tf
5
10
15
20
25
β (˚C /min)
Fig. 3 Linear-fitting plots of cure temperature versus heating rate of MTPES
Table 2 Cure processing
parameters of MTPES by linear-
fitting method
Temperature
Linear expression
R
Cure parameters
(b = 0 °C/min)
Ti
Y = 301 ? 1.242x
Y = 330 ? 2.154x
Y = 355 ? 2.9x
0.9956
0.9692
0.9733
301
330
355
Tp
Te
Curing kinetic analysis of MTPES
The accurate time–temperature-conversion curve is of great practical importance for
establishing optimum cure parameters. Generally, the kinetic parameters can be
calculated using three well-known methods; that is, the Kissinger, Ozawa, and
Flynn–Wall–Ozawa methods [19].
The Kissinger method assumes that the maximum reaction rate occurs at the peak
temperatures [20]. The equation can be expressed as Eq. (1):
ꢀ
ꢁ
b
AR
Ea
Ea
ln ¼ ln
Tp2
À
ð1Þ
RTp
whereb = dT/dt is the heating rate, t is the time, Ea is the activation energy, R is the
universal gas constant, T is the temperature in Kelvin and Tp is the peak tempera-
ture. Figure 6 shows the plot of ln(b/T2p) against 1/Tp for MTPES. The Ea value of
110.38 kJ mol-1 was acquired by Eq. (1).
The Ozawa method assumes that the conversion (a) for different heating rates is
constant [21, 22]. The following Eq. (2) can be applied to the thermal data. Thus,
the plot of lnb versus 1/Tp is a straight line at the same conversion as shown in
Fig. 7. The calculated Ea value was 114.90 kJ mol-1
123

Synthesis, characterization and curing behavior of…
b
a
3500
3000
2500
2000
1500
1000
500
wavenumber (cm-1)
Fig. 4 FT-IR spectra of MTPES (a) and PMTPES (b)
30000
viscosity (Pa.s)
25000
20000
15000
10000
5000
0
150
200
250
300
350
T (˚C)
Fig. 5 Viscosity–temperature curve of MTPES
ꢀ
ꢁ
ꢀ
ꢁ
Ea
RTp
AEa
R
ln b ¼ À5:331 À 1:052
þ ln
À ln fðaÞ
ð2Þ
The Flynn–Wall–Ozawa method [23] is a model-free iso-conversional method,
which assumes that both the activation energy and pre-exponential factor are
functions of the degree of cure based on Eqs. (3) and (4):
123

D. Tan et al.
-9.6
-9.8
y=-13276.22x+10.54
R2=0.9990
-10.0
-10.2
-10.4
-10.6
-10.8
-11.0
-11.2
-11.4
0.00152 0.00154 0.00156 0.00158 0.00160 0.00162 0.00164
1/T
p
Fig. 6 ln(b/T2p) versus 1/Tp of MTPES
3.4
3.2
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
y=-14539.03x+25.43
R2=0.9991
0.00152 0.00154 0.00156 0.00158 0.00160 0.00162 0.00164
1/T
P
Fig. 7 lnb versus 1/Tp of MTPES
ꢀ
ꢁ
ꢀ
ꢁ
AEa
Ea
ln b ¼ ln
À ln gðaÞ À 1:052
À 5:331
ð3Þ
ð4Þ
R
RT
Z
a
da
gðaÞ ¼
fðaÞ
0
Figure 8 shows the temperature versus conversion at different heating rates, and
the corresponding curing parameters are also listed in Table 1. As can be seen, with
123

Synthesis, characterization and curing behavior of…
the increasing of heating rate, the reaction time varies from 3.70 to 11.76 min,
indicating that MTPES has a high reactivity. At the same time, the lnb versus 1/T is
also established in Fig. 9, and the corresponding activation energy is tabulated in
Table 3. The average Ea (112.45 kJ/mol) is very close to the results obtained from
the Kissinger and Ozawa methods, which further verified that acetylene bond can be
initiated in low enthalpy by radical thermal polymerization. As described in the
literature [24], the theoretically predicted enthalpy is 189 10 kJ/mol for
trimerization based on bond energy calculations, while the experimentally
calculated enthalpy is less than the theoretical value, indicating that trimerization
is not the major reaction pathway during polymerization. The most probably
polymerization is a branched polyene, which could then undergo lots of additional
reactions and finally a cross-linked polymer produced [18].
Curing kinetic model analysis of MTPES
In general, the curing mechanism of thermoset is classified into an nth-order
reaction and an autocatalytic reaction [25]. The Friedman method [26] is used
usually to find proper curing mechanism based on Eq. (5):
da Ea
dT RT
ln½Afðaފ ¼ ln b
þ
¼ ln A þ n lnð1 À aÞ
ð5Þ
Therefore, the reaction order n can be obtained from the slope, since the plot of
ln[Af(a)] and ln(1 - a) yields a straight line for the nth-order reaction. Otherwise,
for autocatalytic reaction, the Friedman plot would have a maximum when the
ln(1 - a) is about -0.51 to -0.22 ,corresponding to conversion at about 0.2–0.4.
1.0
5˚C /min
10˚C/min
15˚C/min
0.8
20˚C/min
25˚C/min
0.6
0.4
0.2
0.0
300 310 320 330 340 350 360 370 380 390 400 410 420 430
T (˚C)
Fig. 8 T versus a of MTPES at different heating rates
123

D. Tan et al.
3.4
3.2
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
α=0.05
α=0.10
α=0.15
α=0.20
α=0.25
α=0.30
α=0.35
α=0.40
α=0.45
α=0.50
α=0.55
α=0.60
α=0.65
α=0.70
α=0.75
α=0.80
α=0.85
α=0.90
α=0.95
0.00145
0.00150
0.00155
0.00160
0.00165
0.00170
1/T
Fig. 9 1/T versus lnb of MTPES at different conversions
Table 3 The parameters
obtained from Flynn–Wall–
Ozawa method
a (%)
Ea (kJ/mol)
R
a (%)
Ea (kJ/mol)
111.67
R
5
140.96
124.46
115.00
113.49
116.22
110.62
109.58
110.46
111.33
112.21
0.9662
0.9677
0.9808
0.9883
0.9937
0.9921
0.9977
0.9977
0.9977
0.9977
55
0.9952
0.9962
0.9927
0.9921
0.9921
0.9885
0.9928
0.9893
0.9893
10
15
20
25
30
35
40
45
50
60
113.05
112.36
112.29
113.16
106.87
103.84
98.69
65
70
75
80
85
90
95
100.19
112.45
Mean
This is due to the autocatalytic nature that shows the maximum reaction rate at
20–40 % conversion [27].
Figure 10 depicts Friedman plots of MTPES at different heating rates. Since the
plots of ln[Af(a)] and ln(1 - a) is not linearly related and evidently shows a
maximum in the range of conversion mentioned above, which suggested that the
curing reaction is autocatalytic in nature. The autocatalytic nature of MTPES can be
explained by the generation of free radical of superoxide or hydrogen peroxide,
which is formed by oxygen under at high temperature and these groups accelerate
further cleavage of triple bonds to form conjugated a polyene structure [1, 28].
Owing to the autocatalytic characteristics of the MTPES, the reaction can be
described by Eqs. (6) and (7):
123

Synthesis, characterization and curing behavior of…
20.8
20.4
5˚C/min
10˚C/min
20.0
19.6
19.2
18.8
18.4
18.0
17.6
15˚C/min
20˚C/min
25˚C/min
-4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5
ln (1-α)
Fig. 10 ln[Af(a)] versus ln(1 - a) of MTPES at different heating rates
n
fðaÞ ¼ ð1 À aÞ am
ð6Þ
ð7Þ
ꢀ
ꢁ
da
dT
A
Ea
n
¼
þ
exp À
ð1 À aÞ am
b
RT
then
ꢀ
ꢁ
da
dT
Ea
ln b
¼ n lnð1 À aÞ þ m ln a þ ln A
ð8Þ
RT
where m and n are the reaction orders and m describes the autocatalytic charac-
teristics directly. Equation (8) can be solved by multiple linear regression and the
values of A, m, and n can be obtained using the average activation energy from
different calculated methods, and a is chosen between the beginning of the reaction
and the maximum peak of degree of curing (a = 0.1–0.5). As a result, the
Table 4 The kinetic parameters evaluated for the curing MTPES
b (°C/min)
Ea (kJ/mol)
E = 112.58
lnA (s-1
)
Mean
21.22
n
Mean
1.20
m
Mean
0.56
5
20.60
21.41
21.26
21.01
21.83
0.79
1.13
1.32
0.96
1.78
0.16
0.61
0.61
0.51
0.89
10
15
20
25
123

D. Tan et al.
corresponding result analyses are listed in Table 4. The kinetic mode of MTPES can
be described as follows:
ꢀ
ꢁ
da
dt
112580
1:20
ð1 À aÞ a0:56
¼ e21:22 exp À
RT
Conclusions
Methyl-tri(phenylethynyl)silane (MTPES) was synthesized by Grignard reaction. The
curing schedule of MTPES can be determined as follows: (302 °C, 1 h) ? (331 °C,
2 h) ? (356 °C, 1 h). According to the Kissinger, Ozawa, Flynn–Wall–Ozawa and
Friedman methods, the reaction activation energy and the reaction order n, m were
112.58 kJ/mol, 1.20 and 0.56 respectively. The autocatalytic kinetic model was found
to be the best description of the curing reaction.
Acknowledgments We gratefully acknowledged the financial support of the National Nature Science
Foundation of China (Nos. 51477002, 51303005), the Educational Commission of Anhui Province of
China (Nos. KJ2013A087 and KJ2013A095) and the Doctor Foundation of the Anhui University of
Science and Technology.
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