Full text of DOI:10.1002/kin.20898

Kinetic Study of the
Thermal Polymerization
Reactions between Diazide
and Internal Diyne
RONGPENG LIU, LIQIANG WAN, FARONG HUANG, LEI DU
Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education,
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237,
People’s Republic of China
Received 19 June 2014; revised 16 November 2014; accepted 22 November 2014
DOI 10.1002/kin.20898
Published online 18 December 2014 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: The reaction kinetics between diazide(4,4ꢀ-biphenyl dibenzyl azide) and internal
diyne(bis[2-(phenyl)ethynyl]dimethylsilane) was studied in this study by means of differential
scanning calorimetry (DSC) and nuclear magnetic resonance spectra (1H NMR). DSC was
carried out to analyze the reaction in bulk polymerization condition, whereas 1H NMR for
solution reaction polymerization. The apparent activation energy (eα) calculated by Kissinger’s
method was 90.83 kJ/mol, which was confirmed by Friedman’s method, and 87.67 kJ/mol by 1H
NMR, respectively. The polymerization between the diazide and internal diyne was the second-
order reaction based on calculation from both of DSC and 1H NMR. 2014 Wiley Periodicals,
ꢁC
Inc. Int J Chem Kinet 47: 124–132, 2015
displays, semiconductors, electrolyte membranes, and
high-temperature performance polymers [1,2].
INTRODUCTION
As a classical cycloaddition reaction, Micheal
[3] discovered 1,3-dipolar cycloaddition in 1893,
the reaction formed 1,2,3-triazole from phenyl azide
and dimethyl acelenedicarboxylate. Since then, the
1,3-dipolar cycloaddition between alkyne and azide
group has become an important method to synthesize
1,2,3-triazole compounds and their derivatives [4,5].
The mechanism of 1,3-dipolar cycloaddition between
alkynes and azides was studied by Huisgen in 1960s,
which formed 1,4-disubstituded and 1,5-disubstitued
1,2,3-triazoles [6]. In 1960s, Johson and colleagues
synthesized several linear polytriazoles (PTAs) from
monomers containing both azide and acetylene groups
[7,8]. The obtained PTAs were thermally stable but
Cycloaddition reactions have been employed in poly-
mer synthesis since the mid-1960s, using cycloaddition
reactions for polymerization purposes allows rapid ac-
cess to linear, hyperbranched, and dendritic architec-
tures that feature interesting heterocyclic or strained
multicyclic units within the polymer backbone. Cy-
cloaddition reactions are very efficient and highly se-
lective and allow even stereoselectivity. Polymers pro-
duced via cycloaddition chemistries have found use
in several advanced applications such as liquid crystal
Correspondence to: Liqiang Wan; e-mail: wanliqiang@163.com
C
ꢀ
2014 Wiley Periodicals, Inc.

THERMAL POLYMERIZATION REACTIONS BETWEEN DIAZIDE AND INTERNAL DIYNE
125
hardly processable polymers due to the rigid molecu-
lar chains.
bromoethane (AR), toluene (AR), hydrochloric acid
(AR), dichloromethane (AR), and magnesium sul-
fate (anhydrous, AR) were purchased from Shang-
hai No.1 Reagent Company(Shanghai, China). Sodium
azide (chemical pure (CP)) was purchased from Zhe-
jiang Chengguan Chemical Reagent Factory(Zhejiang,
China). 4,4ꢀ-Dichloromethylbiphenyl (technical pure
(TP)) was purchased from Wuhan Chemical Reagent
Factory(Wuhan, China). Dimethyldichlorosilane and
dimethyl sulfoxide-d6 (DMSO-d6) were obtained from
Aladdin Reagent (Shanghai, China). Phenylacetylent
was obtained from Tokyo Chemical Industry (Shang-
hai, China). THF was refluxed over sodium with ben-
zophenone and freshly distilled in nitrogen before use.
4,4ꢀ-Dichloromethylbiphenyl was recrystallized from
methanol before use. Other chemicals were purchased
and used as received without further purification.
Until 2001, the independent discovery of the
copper(I)-catalyzed alkyne-azide 1,3-cycloaddition
has been obtained by the Meldal [9] and Sharpless [10]
groups; since then, hundreds of papers have appeared
describing the use of this simple “click” methodology
in diverse areas including drug discovery, bioconjugate
chemistry, surface modification, materials preparation,
and polyfunctionalized-building blocks. Its application
in numerous areas has highlighted the value of its
benign reaction conditions, functional tolerance, sim-
ple workup, and purification procedures. Hence, these
long-neglected reactions were suddenly reestablished
in organic synthesis and, in particular, have gained pop-
ularity in materials science nowadays [11–17].
Our laboratory has been engaged in developing
novel low-temperature curing and heat-resistant resins
by the 1,3-dipolar cycloaddition of azide with the
alkyne group since 2002, which were polymerized
at 80°C without Cu(I), a series of PTAs with good
processability and thermal stability has been synthe-
sized [18–22], and a series of novel polytriazoleimides
(PTAIs) containing 1,2,3-triazole has been reported by
thermal or chemical imidization methods, which ex-
hibited high mechanical properties and chemical sta-
bilities and were expected to be used as an advanced
low-temperature molding materials [23,24]. In addi-
tion to PTAs and PTAIs, a novel PTA-based organogel
has been formed by the effects of copper ions due to
the advantages of the “click” reaction [25].
Synthesis of 4,4ꢀ-Biphenyl Dibenzyl
Azide (Diazide)
4,4ꢀ-Biphenyl dibenzyl azide was synthesized accord-
ing to the method described in the literature [22]. 6.30 g
4,4ꢀ-dichloromethylbiphenyl, 6.50 g sodium azide,
20 mL dimethylformamide, and 20 mL toluene were
added into a three-necked round-bottom flask (100 mL)
with a mechanical stirrer and a reflux condenser. The
reaction mixture was slowly heated to 75°C and kept
at this temperature for 6 h. Then the reaction mixture
was poured into a beaker with 200 mL deionized water.
The organic layer was separated, and the aqueous layer
was extracted with 20 mL toluene. The process was re-
peated three times. The organic benzene layers were
combined and dried by anhydrous magnesium sulfate,
and the toluene was then distilled. The spectroscopic
data were consistent with the reported value. mp: 71–
Although the reaction of internal alkyne and azide
cannot be catalyzed by Cu(I), the reaction is also a
useful method to prepare materials [26]. Kinetic stud-
ies and computational calculations have been reported
about the internal alkyne and azide, the second-order
reaction has been applied in this reaction [27–29].
In our previous study, the kinetics of 1,3-dipolar cy-
cloaddition between diazide and different terminal
diynes under thermal but copper-free conditions has
been studied. To improve heat-resistant property, in-
ternal alkyne was used in PTA resins. So in this pa-
per, to deeply understand the 1,3-dipolar cycloaddition
of PTAs, the kinetics of the reaction between diazide
and internal diyne was studied by differential scan-
ning calorimetry (DSC) and nuclear magnetic reso-
1
72°C; FT IR: 2109 cm−1 (–N3); H NMR: (CDCl3,
TMS): 7.39–7.42(d, 4H, Ar-H), 7.26–7.60 (d, 4H, Ar-
H), 4.40 (s, 4H, Ar-CH2N3); 13C NMR: (CDCl3, TMS):
140.86, 135.07, 129.12, 128.88 (Ar), 54.85 (CH2N3);
HRMS (EI, TOF) calcd for C14H12N6 [M]+ 264.1123;
found 264.1125.
Synthesis of Bis
[2-(phenyl)ethynyl]dimethylsilane
(Internal Diyne)
1H NMR), respectively.
nance spectra (
Magnesium powder (2.88 g, 0.12 mol) and dry THF
(30 mL) were added to a round-bottom flask through
mechanical stirring and a condenser pipe. Bro-
moethane (13.08 g, 0.12 mol) dissolved in dry THF
(30 mL) was added dropwise over 1 h to the mag-
nesium suspension under room temperature. Then, the
solution was refluxed for 1 h, after that phenylacetylene
EXPERIMENTAL
Raw Materials
Magnesium powder, hexane (analytical grade (AR)),
tetrahydrofuran (THF), dimethylfomamide (AR),
International Journal of Chemical Kinetics DOI 10.1002/kin.20898

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LIU ET AL.
Figure 1 Synthesis route to 1, 3-dipolar cycloaddition between diazide and internal diyne.
(12.24 g, 0.12 mol) dissolved in dry THF (40 mL) was
added slowly over 1 h under room temperature; the so-
lution was refluxed for 1 h again. Dimethyldichlorosi-
lane (6.19 g, 0.048 mol)dissolved in dry THF (30 mL)
was added in three portions at ambient temperature,
producing a gray-green precipitate; the suspension was
refluxed for 1 h. After this, THF was distilled for about
100 mL. The flask was cooled in an ice bath, and the
reaction was quenched with 2 wt% dilute hydrochlo-
ric acid (50 mL). The solution was extracted with
100 mL toluene; then the organic phase was washed
with be neutral with water, separated, dried (anhydrous
magnesium sulfate), and the solvent was removed in
vacuum. The residue was recrystallized from hexane
(3 × 20 mL) to afford the compound as off-white crys-
tals (9.52 g, 0.025 mol, 75%). mp: 78–79°C; 1H NMR:
(CDCl3, TMS): 7.53–7.56 (m, 4H, Ar-H), 7.31–7.39
(m, 6H, Ar-H), 0.53 (s, 6H, Si(CH3)2); 13C NMR:
(CDCl3, TMS): 132.61, 129.37, 128.72, 123.15 (Ar),
106.43 (Ar–CࣕC), 91.11 (CࣕC–Si), 1.00 (Si–CH3);
HRMS (EI, TOF) calcd for C18H16Si [M]+ 260.1021,
found 260.1020.
Sample Preparation
For DSC kinetic studies, the samples were prepared
by mixing diazide with internal diyne in a 1:1 molar
ratio in 2 mL of dichloromethane at room temperature
using a magnetic stirrer, then the solution was poured
into a clean watch glass to evaporate the solvent. The
samples were obtained after drying under vacuum at
room temperature for 30 min, and prepared samples
were stored in a freezer at –13°C in sealed vials for
subsequent analysis.
1
For H NMR kinetic studies, diazide and internal
diyne were dissolved in a 25-mL round-bottom flask
with 4 mL DMSO-d6 at temperatures ranging from 80
to 110°C through magnetic stirring. And then the step-
growth coupling reactions were monitored. At regular
time intervals, 200 μL of reaction mixture was with-
drawn and dissolved in 0.3 mL of DMSO-d6. The time-
conversion studies were then calculated by integration
of 1H NMR spectra.
RESULTS AND DISCUSSION
Kinetic Study by DSC
Analytical Methods
Proton nuclear magnetic resonance (1H NMR) spectra
were obtained from a Bruker Avance 500 (500 MHz)
NMR spectrometer, and tetramethylsilane (TMS) was
used as an internal standard. DSC measurement was
carried out on a DSC TA Instruments DSC Q2000 spec-
trometer. The heating rate of 5, 10, 15, and 20 °C/min
was chosen for the tests at a flow rate of nitrogen
(50 cm3/min).
The sample of diazide and internal diyne as shown in
Fig. 1 were examined in a DSC cell from 20 to 300°C
at a heating rate of 5, 10, 15, and 20°C/min under
nitrogen atmosphere. Fig. 2 shows a series of dynamic
scanning thermograms for diazide and internal diyne.
As shown in Fig. 2, endothermic peaks appear
around 50°C, which are ascribed to the melting of
the solid reactants. Then the exothermic peaks are
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THERMAL POLYMERIZATION REACTIONS BETWEEN DIAZIDE AND INTERNAL DIYNE
127
Figure 2 DSC thermograms for diazide and internal diyne
at different heating hates.
Figure 3 Kissinger’s analysis for diazide and internal
diyne.
Table I DSC Results of the Diazide and Internal
Diyne Reaction
confirm the accuracy of the Eα calculated by
Kissinger’s method. The most common differential iso-
conversional method is that of Friedman [31], based on
Eq. (2):
Heating rate (β)
(°C/min)
Peak Temperatures, Tp(°C) ꢀH (J/g)
5
157.05
166.65
174.75
179.45
883.4
901.3
836.3
934.0
ꢀ
ꢁ
10
15
20
d α
d t
Eα
ln
= ln[f (α)Aα] −
(2)
RTα
α
For linear nonisothermal programs, Eq. (2) is fre-
quently used in the following form:
observed in the temperature ranging from 100 to
300°C, which is due to the 1,3-dipolar cycloaddition.
The values of reaction heat (ꢀH) obtained from the
scans at different heating rates are slightly different
and summarized in Table I.
ꢀ
ꢁ
d α
d T
Eα
ln β
= ln[f (α)Aα] −
(3)
RTα
α
Generally, with the increment of heating rates, peak
temperatures shift to higher temperatures. Kissinger’s
equation is used to calculate the activation energy as
the equation is described below [30]:
From Eq. (3), the relationship between Eα and
the extent of conversion α can be achieved. The re-
sults are illustrated in Fig. 4 for diazide and internal
diyne.
Fig. 4 indicates that the Eα is stable with the incre-
ment of extent of conversion (α) when α is lower than
80%. Then Eα increases gradually, which is due to the
decomposition of the azide group. The average data of
Eα is 89.61 kJ/mol when α is lower than 80%, which
is very close to the values calculated by Kissinger’s
method.
ꢀ
ꢁ
ꢀ
ꢁ
β
TP2
AR
Eα
Eα
ln
= ln
−
(1)
RTP
In Eq. (1), where R is the universal gas constant, A
is the preexponential factor, β is the heating rate, TP
is the peak temperatures, and ln(AR/Eα) is a constant.
2
So a plot of ln(β/TP ) against 1/TP yields values for
The DSC method not only provides the value of Eα
but also indicates further details of reaction kinetics
such as reaction order through model fitting.
Eα from the slope of the liner fit with a coefficient of
determination R2 > 0.99, as shown in Fig. 3. The Eα
of diazide and internal diyne reaction are calculated as
90.83 kJ/mol.
Besides using Kissinger’s equation, the differen-
tial isoconversional method was also employed to
ꢀ
ꢁ
dα
dT
Ea
β
= A exp −
(1 − α)n
(4)
RT
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LIU ET AL.
To simplify the calculation, the constant value of
Eα from Kissinger’s analysis is considered in Eq. (4).
A plot of ln[β(dα/dT)] + ln(Eα/RT) against ln(1–α)
yields values for the preexponential factor A and re-
action orders n from the intercept and slope of the
liner fit, respectively. Fig. 5 demonstrates the nth-order
model-fitting curves of diazide and internal diyne reac-
tion at 5, 10, 15, and 20°C/min, respectively. In these
cases, the model curves are consistent with the ex-
perimental data; whereas at the end of the reaction,
the model curves deviate from the experimental data,
which are ascribed to the change in Eα as shown in
Fig. 4.
The kinetic parameters for bulk polymerization of
diazide and internal diyne are calculated and listed
in Table II. As discussed above, the reaction of di-
azide and internal diyne meets the nth-order model,
which shows a near second-order reaction characteris-
tic. In our previous study, the kinetics of diazide and
two terminal diynes was studied [32]; the Eα of di-
azide and internal diyne is a little higher than those of
diazide and terminal diynes because of maybe larger
Figure 4 Relationship between Eα and α for diazide and
internal diyne.
The reaction model described as Eq. (4) [from
Eq. (3)] can be used to fit the experimental data, which
can be used to obtain the reaction order, n.
Figure 5 The nth model fits of diazide and internal diyne at (a) 5°C/min, (b) 10°C/min, (c) 15°C/min, and d) 20°C/min.
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THERMAL POLYMERIZATION REACTIONS BETWEEN DIAZIDE AND INTERNAL DIYNE
129
Table II Summary of the Kinetic Parameters of Diazide
and Internal Diyne Reaction
Table III Observed Rate Orders in the Variable
Component Derived from Kinetic Measurementsa
[Internal Diyne] [Diazide]
Sample
A (×10)a
2.90
2.88
2.90
2.76
na
Eb(kJ/mol) Ec(kJ/mol)
Component
[M]
[M]
Rate Order
5°C/min
1.69
1.75
1.74
1.65
Internal diyne
diazide
0.5–1.5
0.5
0.5
0.5–1.5
0.82
0.75
10°C/min
15°C/min
20°C/min
90.83
89.61
aReactions were performed at 100 1°C in DMSO.
aValues from the fitting parameters of original experimental data.
bCalculated from Kissinger’s method.
cCalculated from Friedman’s method.
Kinetic Study by 1H NMR
To study the reaction kinetics via solution polymer-
1
ization, H NMR is used to determine the changes in
monomers during the 1,3-dipolar cycloaddition.
steric hindrance of internal diyne or a different reaction
mechanism. For diazide and terminal diynes, the re-
actions are both first-order reactions, which indi-
cates that the reaction between diazide and internal
diyne, diazide, and terminal diyne possesses different
mechanisms.
As shown in Fig. 6, through changing a single re-
actant, the contribution of internal diyne and diazide
for the reaction is calculated, respectively. By means of
plotting the initial reaction rate against reactant conver-
sion, the reaction orders of internal diyne and diazide
shown in Table III are both near first orders, which
Figure 6 Kinetic measurements: (a) the relationship between [azide] and monomer conversion, (b) rate-order plots showing
the first-order dependence on [azide], (c) the relationship between [internal diyne] and monomer conversion, and (d) rate-order
plots showing the first-order dependence on [internal diyne].
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LIU ET AL.
Figure 7 Evolution of 1H NMR spectra (DMSO-d6, [internal diyne]/[azide] = 1.6:1.0, and T = 100°C) during the synthesis
of diazide and internal diyne.
implies that the 1,3-dipolar cycloaddition of internal
diyne and diazide is a second-order reaction.
In detail, the polymerization kinetics of a 1:1 molar
ratio of diazide and internal diyne in DMSO-d6 was
1
monitored by H NMR spectroscopy at 80, 90, 100,
and 110°C, respectively. The reaction evolution of the
1,3-dipolar cycloaddition between diazide and inter-
nal diyne is shown in Fig. 7. For diazide and internal
diyne, the reaction was confirmed by the signal shift
from methylene groups adjacent to azide (at 4.40 ppm)
toward the methylene protons adjacent to the formed
triazole rings (at 5.34, 5.45, 5.65 ppm).
Conversion ratios of the monomers are calculated
1
by integration of the H NMR spectra. Following the
evolutions azide and triazole signals, the reaction de-
gree can be described as follows:
Figure 8 1H NMR monitoring (DMSO-d6, 0.5 mol/L of
monomers at T = 80, 90, 100, and 110°C) for the reaction of
Ia1 + Ia2 + Ia3
a =
diazide and internal diyne.
IA + Ia1 + Ia2 + Ia3
where α is the conversion at t time, and Ia1, Ia2, and
Ia3 are the integration of signal related to methylene
protons adjacent to the formed triazole rings, whereas
IA is the integration of signal corresponding to the
methylene groups adjacent to azide. The conversion
rates of a triazole unit at 80, 90, 100, and 110°C for
diazide and internal diyne are presented in Fig. 8.
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THERMAL POLYMERIZATION REACTIONS BETWEEN DIAZIDE AND INTERNAL DIYNE
131
Table IV Summary of the Kinetic Parameters of
Internal Diyne and Diazide under Different Temperatures
Temperature (°C)
k (M−1·h−1
)
R2
80
90
100
110
0.01598
0.02901
0.07688
0.1562
0.99
0.99
0.99
0.99
quite different from the reaction for diazide and termi-
nal diynes. Both of the reactions between diazide and
terminal diynes are the first-order reactions, whereas
diazide and internal diyne is a second-order reaction.
The reason of the different reaction orders of internal
alkyne/azide and terminal alkyne/azide is the different
rate-determining steps for the concerted 1,3-dipolar
cycloaddition. Achieving a transition state geometry
requires significant distortion of the dipole and the
dipolarophile distortion. For an internal alkyne/azide
reaction, due to the lager steric hindrance of internal
alkyne, its distortion is much difficult than that of ter-
minal alkyne; the rate-determining step changes and
causes different reaction mechanism. Furthermore, for
diazide and terminal diynes, owing to faster mobil-
ity of monomers and more effective molecular col-
lisions, the functional groups have much higher re-
activity in the solution. Then the obtained Eα from
1H NMR are much lower than those form DSC, is
about 10 kJ/mol. However, in the reaction of diazide
Figure 9 Second-order linearization plots for the synthe-
sis of diazide and internal diyne (DMSO-d6, 0.5 mol/L of
monomers at T = 80, 90, 100, and 110°C), where α is the
monomer conversion.
Moreover, as shown in Figs. 9 and 10, the second-
order linearization of the time-conversion plots pro-
vides the determination of the overall polymerization
rate constant k for each temperature. Arrhenius’ plot of
these data with a coefficient of determination R2 > 0.99
allows calculation of the Eα of the 1,3-dipolar cycload-
ditions, which is 87.67 kJ/mol for diazide and internal
diyne. All the kinetic parameters are summarized in
Table IV.
1
Kinetic parameters calculated with H NMR anal-
1
and internal diyne, the Eα from H NMR is a little
ysis are consistent with that achieved by means of the
DSC method. However, the reaction order and Eα are
lower (about 2 kJ/mol) than that from DSC; the re-
sult implies that the polymerization carried out in the
solution reaction is not easier than that of terminal
diynes.
CONCLUSIONS
The reaction kinetic of bulk and solution polymeriza-
tion without copper catalysts between diazide and in-
ternal diyne was studied by DSC and 1H NMR, respec-
tively. The results show that
1
(a) the Eα obtained from H NMR spectra was
close to that by the DSC method, about
10 kJ/mol is higher than the reactions for di-
azide and terminal diynes;
(b) The reaction for diazide and internal diyne is
a second-order reaction, which is totally dif-
ferent from the first-order reaction for diazide
and terminal diynes, described in the literature
before.
Figure 10 ln k-T−1 plots for the reaction of diazide and
internal diyne.
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LIU ET AL.
The authors gratefully acknowledge the financial support of
Shanghai Leading Academic Discipline Project (B502) and
Fundamental Research Funds for the Central University.
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International Journal of Chemical Kinetics DOI 10.1002/kin.20898