polymers

Communication
Thermal Degradation Behavior of Thiol-ene Composites
Loaded with a Novel Silicone Flame Retardant
Haonan Chen 1 , Sheng Zhu 1 , Rongfan Zhou 1 , Xintong Wu 1 , Wangyang Zhang 1 , Xiaoshuai Han 2, *
and Jiangbo Wang 1,3, *

1 School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, China
2 Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International
Innovation Center for Forest Chemicals and Materials, College of Materials Science and Engineering, Nanjing
Forestry University, Nanjing 210037, China
3 Zhejiang Institute of Tianjin University, Ningbo 315201, China
* Correspondence: [email protected] (X.H.); [email protected] (J.W.)

Abstract: A novel silicone flame retardant PMDA was synthesized and blended with a commercial
thiol–ene (TE) to obtain a flame-retardant TE (FRTE) composite. The cone calorimeter measure-
ment showed the incorporation of PMDA improved the flame retardancy of the TE composite at
concentrations of 5 wt%. The thermal stability and degradation mechanism of FRTE in nitrogen
was studied by thermogravimetric analysis. The degradation behaviour of TE containing a PMDA
flame retardant was found to be changed. The kinetics of thermal degradation was evaluated by
Kissinger method and Flynn–Wall–Ozawa method. The results showed that the activation energies
of the FRTE degradation were higher than those of neat TE. However, the degradation mechanism
of the TE matrix was not changed by the incorporation of flame-retardant PMDA. In this study,
the flame-retardant mechanism of PMDA flame-retardant TE polymer was explained by using two
kinetic analysis methods.
Citation: Chen, H.; Zhu, S.; Zhou, R.;
Wu, X.; Zhang, W.; Han, X.; Wang, J. Keywords: flame retardancy; thiol-ene; PMDA; thermal degradation
Thermal Degradation Behavior of
Thiol-ene Composites Loaded with a
Novel Silicone Flame Retardant.
Polymers 2022, 14, 4335. https:// 1. Introduction
doi.org/10.3390/polym14204335
With the continuous progress of research work, various polymerization methods and
Academic Editors: Marcos Batistella composite preparation technologies have been developed rapidly [1–3]. Photopolymeriza-
and Laurent Ferry tion is a rapid, inexpensive and simple technique for producing cross-linked materials with
thicknesses ranging from a few microns to several millimeters. It is widely used in several
Received: 19 September 2022
applications such as coatings, adhesives, paints, inks, microelectronics, optical materials
Accepted: 11 October 2022
Published: 14 October 2022
and dental resins. Because of its many advantages over other polymerization processes
including low energy consumption, solvent-free resin compositions, high curing speed and
Publisher’s Note: MDPI stays neutral ambient temperature processing, it is considered as a “green” technology [4–6].
with regard to jurisdictional claims in As a new kind of photopolymerization system, photopolymerized thiol–ene (TE)
published maps and institutional affil-
networks have attracted much interest in academia as well as industries due to unique
iations.
advantages, such as narrow glass transitions, low shrinkage, and 90% functional group
conversion. Thiol–ene photopolymerization is a free radical process rather than a typical
chain growth reaction. This photopolymerization is very low under the influence of an
oxygen environment and has excellent polymerization stability. However, the flammability
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
of thiol–ene is a serious limitation in areas requiring high flame retardancy [7–11].
This article is an open access article
In recent years, some different approaches have been reported, and the introduction
distributed under the terms and of boron- and phosphorus-containing compounds into thiol–ene has been shown to be an
conditions of the Creative Commons effective way of improving its flame retardancy [12,13]. Silicon-containing compounds are
Attribution (CC BY) license (https:// demonstrated to be one of the choices for use as flame retardants because of their excellent
creativecommons.org/licenses/by/ properties, such as high resistance to thermal oxidation, imparting nonflammability, low
4.0/). glass transition temperature, environmental friendliness and low surface energy to the

Polymers 2022, 14, 4335. https://doi.org/10.3390/polym14204335 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, x FOR PEER REVIEW 2 of 9

are demonstrated to be one of the choices for use as flame retardants because of their ex-
Polymers 2022, 14, 4335 cellent properties, such as high resistance to thermal oxidation, imparting nonflammabil- 2 of 9
ity, low glass transition temperature, environmental friendliness and low surface energy
to the resin [14–17]. Based on this concept, silicon-containing compounds are expected to
beresin
one[14–17].
of the choices
Based on forthis
enhancing the flame retardancy
concept, silicon-containing of the thiol–ene
compounds are expected systems. Theof
to be one
methyl group in the structure of silicon-containing compounds can
the choices for enhancing the flame retardancy of the thiol–ene systems. The methyl group improve the migration
performance
in the structureof a of
flame retardant during
silicon-containing combustion,
compounds canwhile
improvethe phenyl group can
the migration increase
performance
the
of charring performance,
a flame retardant during socombustion,
as to achievewhile efficient
the flame
phenylretardancy.
group can increase the charring
The flame so
performance, retardancy
as to achieveof polymer
efficient is flame
closelyretardancy.
related to its thermal degradation process,
whichThe is a flame
chain-breaking
retardancyprocess caused
of polymer by highrelated
is closely temperatures or long-time
to its thermal actionprocess,
degradation in the
absence of oxygen. In general, thermal degradation is related to
which is a chain-breaking process caused by high temperatures or long-time action in thethe chemical bond energy
ofabsence
polymers. The higher
of oxygen. the chemical
In general, thermal bond energy, the
degradation is less likely
related to it is chemical
the to be degraded. GC-
bond energy
MS, GC-FTIR, The
of polymers. etc.,higher
can bethe used for thermal
chemical degradation
bond energy, the lessstudies
likely it[18,19].
is to beIndegraded.
the present GC-
work, a novel silicone
MS, GC-FTIR, etc., canflame-retardant
be used for thermal PMDA was synthesized
degradation and introduced
studies [18,19]. intowork,
In the present the
thiol–ene. PMDA flame-retardant
a novel silicone contains methyl,PMDA phenylwas andsynthesized
amino groups andinintroduced
the structure, intoforming a
the thiol–
ene. network
body PMDA contains
structure, methyl,
so thatphenyl and amino
it has excellent flamegroups in the structure,
retardancy forming a per-
and char formation body
network in
formance structure, so that
combustion. it hasthe
Here, excellent flame retardancy
flame retardancy and char
and thermal formation behavior
degradation performance of
a in combustion. Here,
thiol–ene/PMDA the flame
composite were retardancy
investigated and bythermal degradationand
cone calorimeter behavior of a thiol–
TGA measure-
ene/PMDA
ments, composite were investigated by cone calorimeter and TGA measurements,
respectively.
respectively.
2. Materials and Methods
2. Materials and Methods
2.1. Materials
2.1. Materials
Dimethyldimethoxysilane (DMDS) and phenyltrimethoxysilane (PTMS) of reagent
Dimethyldimethoxysilane (DMDS) and phenyltrimethoxysilane (PTMS) of reagent
grade were supplied from Gelest Chemical Reagent Co., Ltd. (Morrisville, PA, USA). Me-
grade were supplied from Gelest Chemical Reagent Co., Ltd. (Morrisville, PA, USA).
thyltrimethoxysilane (MTMS), tetramethylammonium hydroxide (TMAOH) and (3-ami-
Methyltrimethoxysilane (MTMS), tetramethylammonium hydroxide (TMAOH) and (3-
nopropyl)trimethoxysilane (APS) were all provided by Alfa Aesar Chemical Reagent Co.
aminopropyl)trimethoxysilane (APS) were all provided by Alfa Aesar Chemical Reagent
Ltd. (Tewksbury, MA, USA). Trimethylolpropane tris(3-mercaptopropionate) (3T) was
Co. Ltd. (Tewksbury, MA, USA). Trimethylolpropane tris(3-mercaptopropionate) (3T) was
obtained
obtainedfrom fromBruno
BrunoBock BockChemische
ChemischeFabrik FabrikGmblt
Gmblt&&Co. Co.(Marschacht,
(Marschacht,Germany)
Germany)and and
used as received. Ethyl alcohol (EtOH), 2,2-dimethoxy-2-phenylacetophenone
used as received. Ethyl alcohol (EtOH), 2,2-dimethoxy-2-phenylacetophenone (DMPA) (DMPA) and
and pentaerythritol allyl ether (TAE) were purchased from
pentaerythritol allyl ether (TAE) were purchased from Sigma-Aldrich Reagent Co. Ltd.Sigma-Aldrich Reagent Co.
Ltd.
(St. (St. Louis,
Louis, MO,MO, USA).USA).

2.2.
2.2.Synthesis
SynthesisofofSilicone
Silicone(PMDA)
(PMDA)
The
Thesilicone
siliconesample
sample was prepared
preparedby byhydrolysis
hydrolysisand
andcondensation
condensation method,
method, which
which was
was composed
composed of 60ofmol%
60 mol% phenylsiloxane,
phenylsiloxane, 35 mol% 35 methylsiloxane
mol% methylsiloxane and 5aminosiloxane.
and 5 mol% mol% ami-
nosiloxane.
The ratio ofThe ratiogroup
organic of organic group
to silicon to silicon
atom (R/Si)atom (R/Si)
was 1.2, was 1.2,the
indicating indicating the
degree of degree
branching
ofofbranching of polysiloxane structure. The structure of silicone
polysiloxane structure. The structure of silicone is shown in Figure 1.is shown in Figure 1.

SynthesisofofPMDA.
Figure1.1.Synthesis
Figure PMDA.

In a 250 mL flask, distilled water (25 mL), EtOH (75 mL) and TMAOH (1 mL) were
added and stirred. Then, a molar ratio (0.69:0.06:0.20:0.05) of PTMS, MTMS, DMDS and
APS mixture was added to the solution, and the total weight percentage was maintained at
Polymers 2022, 14, x FOR PEER REVIEW 3 of 9

Polymers 2022, 14, 4335 In a 250 mL flask, distilled water (25 mL), EtOH (75 mL) and TMAOH (1 mL) were 3 of 9
added and stirred. Then, a molar ratio (0.69:0.06:0.20:0.05) of PTMS, MTMS, DMDS and
APS mixture was added to the solution, and the total weight percentage was maintained
at 10 wt%. The solution was stirred for 8 h and left overnight. The precipitated condensate
10 wt%. The solution was stirred for 8 h and left overnight. The precipitated condensate
was collected by decanting the clearest supernatant, washed by vacuum filtration with
was collected by decanting the clearest supernatant, washed by vacuum filtration with
distilled water/EtOH (1/3 by volume), and then washed again in pure EtOH. The powder
distilled water/EtOH (1/3 by volume), and then washed again in pure EtOH. The powder
(PMDA) was dried and rinsed thoroughly under vacuum for 20 h at room temperature.
(PMDA) was dried and rinsed thoroughly under vacuum for 20 h at room temperature.
2.3. Preparation of Thiol-ene Composites
2.3. Preparation of Thiol-ene Composites
The preparation method of TE/PMDA (FRTE) composite was as follows: The pho-
The preparation method of TE/PMDA (FRTE) composite was as follows: The pho-
toinitiator (DMPA, 1 wt%) was dissolved in mercaptan (3 T), and ultrasonically treated
toinitiator (DMPA, 1 wt%) was dissolved in mercaptan (3 T), and ultrasonically treated
for 30 min. Then, TAE (1:1, equal to thiol) and PMDA (5 wt%) were added into the mixed
for 30 min. Then, TAE (1:1, equal to thiol) and PMDA (5 wt%) were added into the mixed
solution, and stirred with a glass rod for 1 min. After further mixing and the removal of
solution, and stirred with a glass rod for 1 min. After further mixing and the removal of
bubbles (30 min) ultrasonically, a wire drawing rod was used to pull the uniform mixture
bubbles (30 min) ultrasonically, a wire drawing rod was used to pull the uniform mixture
onto the glass substrate. The film was cured 10 times under a fused UV-curing line system,
onto the glass substrate. The film was cured 10 times under a fused UV-curing line system,
under D bulb (400 W/cm22, belt speed 3 m/min, irradiance 3.1 W/cm2).2In order to facilitate
under D bulb (400 W/cm , belt speed 3 m/min, irradiance 3.1 W/cm ). In order to facilitate
comparison, neat TE was also prepared under the same processing conditions.
comparison, neat TE was also prepared under the same processing conditions.
2.4.
2.4. Characterization
Characterization and
andMeasurement
Measurement
Cone
Cone calorimeter measurementswere
calorimeter measurements wereperformed
performedon onananFTT
FTTcone
conecalorimeter
calorimeter(Fire
(Fire
Testing Technology Ltd., East Grinstead, West Sussex, UK) with heat fluxof
Testing Technology Ltd., East Grinstead, West Sussex, UK) with heat flux of50
50kW/m
2
kW/m2
according to ASTM E1354. The size of each specimen was 100 × 100 × 3 mm
according to ASTM E1354. The size of each specimen was 100 × 100 × 3 mm . Thermo-
3. Thermograv-
3
imetric analysis
gravimetric (TGA)
analysis was performed
(TGA) on a TA
was performed on ainstrument Q5000Q5000
TA instrument thermogravimetric an-
thermogravimetric
alyzer (TA instrument company, New Castle, DE, USA). The sample (approximately
analyzer (TA instrument company, New Castle, DE, USA). The sample (approximately 10
mg) was heated in a nitrogen atmosphere from 50 °C to
◦ 600 °C at
◦ a set heating
10 mg) was heated in a nitrogen atmosphere from 50 C to 600 C at a set heating rate. rate.

3. Results
Results and
and Discussion
Discussion
Flame Retardancy
3.1. Flame Retardancy
The cone
The cone calorimetry
calorimetryusesusesan anoxygen
oxygenconsumption
consumptioncalorimeter
calorimeter toto measure
measure thethe com-
com-
bustion rate
bustion rateand andamount
amountofofheating.
heating. Because
Because thethe
testtest process
process is very
is very closeclose
to thetoactual
the actual
fire
fire situation,
situation, it is it is one
one of most
of the the most effective
effective experimental
experimental methods
methods to study
to study the combus-
the combustion
tion characteristics
characteristics of polymer
of polymer materials.
materials. Figure
Figure 2 illustrates
2 illustrates the the plots
plots of of heat
heat release
release rate
rate
(HRR) and total
total heat
heat release
release(THR)
(THR)versus
versusthethetemperature
temperatureofofthe theTE
TEcomposites.
composites.The The neat
neat
TE exhibited 2 and a THR of
exhibited aa higher
higher peak
peak ofof heat
heat release
release rate
rate (PHRR)
(PHRR)of of2152.4
2152.4kW/m
kW/m 2 and a THR of
188.0 MJ/m 2 . For the FRTE composite, the PHRR was significantly suppressed by 39.4%,
MJ/m . For the FRTE composite, the PHRR was significantly suppressed by 39.4%,
2

2152.4kW/mkW/m 2 to 1304.9 kW/m 2 . Further reduction of THR from 188.0 2MJ/m2 to

from 2152.4 2 to 1304.9 kW/m2. Further reduction of THR from 188.0 MJ/m to 140.3
140.3 2
MJ/m MJ/m
2 was observed
was observed for FRTE,
for FRTE, which which was reduced
was reduced by 25.4%.
by 25.4%. The decrease
The decrease of HRR ofand
HRR
and THR
THR indicated
indicated thatthat
the the incorporation
incorporation of PMDA
of PMDA intointo polymer
polymer composites
composites could
could restrict
restrict
development [20,21].
fire development [20,21].

(a) (b)
Figure
Figure 2.
2. The
The heat
heat release
releaserate
rate(a)
(a)and
andtotal
totalheat
heatrelease
release(b)
(b)curves
curvesfor
forTE
TEcomposites.
composites.

3.2. Thermal Stability

The fire resistance of materials is closely related to its thermal stability. Currently,
TGA is one of the most widely used techniques to rapidly assess the thermal stability of
Polymers 2022, 14, x FOR PEER REVIEW 4 of 9

3.2. Thermal Stability

Polymers 2022, 14, 4335 4 of 9
The fire resistance of materials is closely related to its thermal stability. Currently,
TGA is one of the most widely used techniques to rapidly assess the thermal stability of
various polymer composites. The thermal properties of TE and FRTE were studied by
various polymer composites. The thermal properties of TE and FRTE were studied by TGA
TGA at heating rates of◦ 10 °C/min under N2 atmosphere, as shown in Figure 3 and Table
at heating rates of 10 C/min under N2 atmosphere, as shown in Figure 3 and Table 1. It
1. It can be seen that the onset degradation temperature (T5wt%) of neat TE occurred at
can be seen that the onset degradation temperature (T5wt% ) of neat TE occurred at about
about 345.7 °C. With the incorporation of 5 wt% PMDA, the T5wt% of FRTE dropped to
345.7 ◦ C. With the incorporation of 5 wt% PMDA, the T5wt% of FRTE dropped to 316.1 ◦ C,
316.1 °C, this was due
this was mainly mainly due
to the to the condensation
condensation reaction reaction of residual
of residual silanols
silanols and and meth-
methoxy groups
oxy groups on PMDA. However, the temperature of the peak rate (T max) for FRTE was
on PMDA. However, the temperature of the peak rate (Tmax ) for FRTE was slightly higher
slightly higher
than that than
of neat TE,that
andofthe
neat TE,degradation
main and the main degradation
of TE compositesofwas
TE shifted
composites was
to a higher
shifted to a higher
temperature temperature
by the introductionbyof
the introduction of PMDA.
PMDA.

Thermalstability
Figure3.3.Thermal
Figure stabilityofofTETEcomposites.
composites.

Table 1. TGA data of TE composites.

Table 1. TGA data of TE composites.
Temperature (◦ C) Peak Rate Residue
Residue
Sample Temperature (°C) Peak Rate CharChar
Sample T 5wt% Tmax (wt%/◦ C) (wt%)
T5wt% Tmax (wt%/°C) (wt%)
TE
TE 345.7
345.7 385.9 385.9 1.95 1.95 1.33 1.33
FRTE 316.1 387.8 1.73 3.37
FRTE 316.1 387.8 1.73 3.37

Moreover,aa significant
Moreover, significant increase
increaseinincharring
charring was observed
was in the
observed FRTE,
in the which
FRTE, increased
which in-
creased by 2% compared with the neat TE. Therefore, it was apparent from Figure 3PMDA
by 2% compared with the neat TE. Therefore, it was apparent from Figure 3 that the that
offered
the PMDA significant advantages
offered significant in the charinformation
advantages of TE composite.
the char formation of TE composite.
3.3. Thermal Degradation Kinetics
3.3. Thermal Degradation Kinetics
The thermal stability of polymer is related to its initial temperature and degradation
The thermal stability of polymer is related to its initial temperature and degradation
rate. Therefore, the kinetic analysis method can be used to calculate the kinetic parameters
rate. Therefore, the kinetic analysis method can be used to calculate the kinetic parameters
in the degradation process of the system, which helps to study the thermal stability of
in the degradation process of the system, which helps to study the thermal stability of the
the materials. The Kissinger method and Flynn–Wall–Ozawa method are derived from
materials. The Kissinger method and Flynn–Wall–Ozawa method are derived from the
the basic kinetic equation of a multiphase chemical reaction. When obtaining the relevant
basic kinetic equation of a multiphase chemical reaction. When obtaining the relevant ki-
kinetic parameters, they do not need to determine the reaction order and conversion
netic parameters, they do not need to determine the reaction order and conversion func-
function, which is very convenient. Therefore, this study will use these two methods to
tion, which is very convenient. Therefore, this study will use these two methods to calcu-
calculate the kinetic parameters of composite materials.
late the kinetic parameters of composite materials.
TGA and DTG curves of TE composites in a nitrogen atmosphere were measured at
heating rates of 5, 10, 20 and 40 ◦ C/min. As the heating rate increased (Figures 4 and 5), the
thermograms shifted to the higher temperature region. At a low heating rate, it was easy to
reach equilibrium at any point with the increase of temperature. When the heating rate was
too fast, due to slow diffusion of heat, the equilibrium was slow, the curve shifted to the
 TGA and DTG curves of TE composites in a nitrogen atmosphere were measured at
TGA and DTG curves of TE composites in a nitrogen atmosphere were measured at
heating rates of 5, 10, 20 and 40 °C/min. As the heating rate increased (Figures 4 and 5),
heating rates of 5, 10, 20 and 40 °C/min. As the heating rate increased (Figures 4 and 5),
Polymers 2022, 14, 4335 the thermograms shifted to the higher temperature region. At a low heating rate, it was 5 of 9
the thermograms shifted to the higher temperature region. At a low heating rate, it was
easy to reach equilibrium at any point with the increase of temperature. When the heating
easy to reach equilibrium at any point with the increase of temperature. When the heating
rate was too fast, due to slow diffusion of heat, the equilibrium was slow, the curve shifted
rate was too fast, due to slow diffusion of heat, the equilibrium was slow, the curve shifted
to the high temperature region, and therefore the degradation point (or degradation tem-
to the temperature
high high temperature
region,region, and therefore
and therefore the degradation
the degradation point point (or degradation
(or degradation tem-
temperature)
perature) was high.
perature)
was high. was high.

(a) (b)
(a) (b)
Figure 4. TGA curves of TE (a) and FRTE (b) composites.
Figure
Figure4.4.TGA
TGAcurves
curvesofofTE
TE(a)
(a)and
andFRTE
FRTE(b)
(b)composites.
composites.

(a) (b)
(a) (b)
Figure
Figure5. DTG
DTGcurves
curvesof TETE(a)
(a)and
andFRTE
FRTE(b)
(b)composites.
Figure 5.5.DTG curves ofofTE (a) and FRTE (b) composites.
composites.

Kineticanalysis
Kinetic analysisofofthermal
thermaldegradation
degradationis is one
one ofof the
the potential
potential methods
methods to to solve
solve this
this
Kinetic analysis of thermal degradation is one of the potential methods to solve this
problem.The
problem. Thekinetic
kineticparameters
parametersofofthethewhole
whole degradation
degradation process
process were
were calculated
calculated bybythethe
problem. The kinetic parameters of the whole degradation process were calculated by the
Kissingermethod.
Kissinger method.The
Thecalculation
calculationequation
equationofofthe
the Kissinger
Kissinger method
method is is
asas follows
follows [22]:
[22]:
Kissinger method. The calculation equation of the Kissinger method is as follows [22]:
β AR EE
ln(( T222 ))) = ln(AR )))−
AR
ln(
ln ==ln(
ln( − E
− (1)(1)
(1)
max
Tmax
max EEE RT
RTmax
max
RTmax
where
whereβββis the
theheating
heatingrate,
rate,A is the
thepre-exponential factor, RRis thethe
universal gasgas
constant
where isisthe heating rate, AAisisthe pre-exponential
pre-exponential factor,
factor, R is is universal
the universal constant
gas constant
and
and EEis
isthe
the apparent
apparent activation
activation energy
energyof
ofthe
thekinetic
kinetic process.
process.
and E is the apparent activation energy of the kinetic process.
The fitting lines of ln( T 1 1
2 ) verse Tmax1for the TE composites at various heating rates
β
The fitting lines of ln( max ) verse
ln(T 22 parameters for the TE composites at various heating
) verse Tcalculated
and The fitting lines of kinetic
the corresponding for thebyTE
thecomposites at various
Kissinger method areheating
shown in
Figure 6 and Table 2.
T max
max Tmax
max
rates and the corresponding kinetic parameters calculated by the Kissinger method are
rates and the corresponding kinetic parameters calculated by the Kissinger method are
shown in Figure 6 and Table 2.
shown in Figure 6 and Table 2.
Polymers 2022, 14, x FOR PEER REVIEW 6 of 9
Polymers 2022, 14, 4335 6 of 9

1

β
Figure 6. ln( T2 ) vs. curves of TE and FRTE.
max T max 1
Figure 6. ln( 2 ) vs. curves of TE and FRTE.
Tmaxdata for TE
Table 2. Kinetic Tmax
and FRTE degradation by the Kissinger method.

Temperature (◦ C) lnA
Table 2. Kinetic data for TE and FRTE degradation by the Kissinger method.
E (kJ/mol)
5 ◦ C/min 10 ◦ C/min 20 ◦ C/min 40 ◦ C/min (1/min)
TE 367.5
Temperature
385.9
(°C)407.5 433.4E (kJ/mol)
107.4 lnA (1/min)
11.4
FRTE5 °C/min
369.6 10 °C/min
387.8 20 °C/min408.740 °C/min433.0 112.5 12.4
TE 367.5 385.9 407.5 433.4 107.4 11.4
FRTE 369.6 387.8 408.7 433.0 112.5
As shown in Table 2, the E values of the neat TE and FRTE composites were 12.4 about
107.4 and 112.5 kJ/mol, respectively. The preexponential factors, A, were about 11.4 × 1010
and As
12.4shown
× 1010in TableIt2,could
/min. the Ebe values of thefrom
obtained neatthe
TEincrease
and FRTE in composites
the apparent were about
activation
107.4
energy of the TE degradation that PMDA could improve the thermal degradation ×of10TE
and 112.5 kJ/mol, respectively. The preexponential factors, A, were about 11.4 10

and 12.4 × 10
composite but/min.
10 It could
did not change bethe
obtained from the
degradation increase of
mechanism in TE
thematrix
apparent activation en-
[23].
ergy of
In order to calculate the degradation kinetics in more detail, the TGA dataofwere
the TE degradation that PMDA could improve the thermal degradation TE com-
also
posite but did not change the degradation mechanism of TE matrix
calculated using the Flynn–Wall–Ozawa method. The Flynn–Wall–Ozawa method is not [23].
onlyIn order to
a typical calculate the
model-free degradation
method, but alsokinetics in more
a relatively simpledetail,
and the TGA data
convenient were also
method. The
calculated using the
activation energy Flynn–Wall–Ozawa
of the system can be quicklymethod. The Flynn–Wall–Ozawa
calculated and determined only method is not
by obtaining
only a typical
the data model-free
of weight loss andmethod, but also
temperature a relatively
of TGA curves atsimple andheating
different convenient
rates.method.
The activation
The equationenergy of the system can method
of Flynn–Wall–Ozawa be quicklyis ascalculated and determined only by
follows [24,25]:
obtaining the data of weight loss and temperature of TGA curves at different heating rates.
The equation of Flynn–Wall–Ozawa E
lg( β) = lgAE/g(method is as−
a) R − 2.315 follows
0.457 [24,25]: (2)
RT
E
According to Equation lg((2),
) = the
lg AE − 2.315can
/ g (a) Renergies
activation − 0.457
be calculated by linear fitting(2)of
RT
lg( β) verse 1/T plot at different conversion degree. It can be seen from Figure 7 that the
According to Equation (2), the activation energies can be calculated by linear fitting
fitting lines of the TE and FRTE composites were almost parallel, indicating their unique
of lg(  ) verse
degradation 1/ T plotThat
mechanism. at different
was, PMDAconversion
did not degree. It degradation
affect the can be seen from Figure of
mechanism 7
that the fitting
TE, which waslines of the
similar TE results
to the and FRTE
fromcomposites were
the Kissinger almost parallel, indicating their
method.
unique degradation mechanism. That was, PMDA did not affect the degradation mecha-
nism of TE, which was similar to the results from the Kissinger method.
Polymers
Polymers 2022,
2022, 14,
14, x4335
FOR PEER REVIEW 7 of79of 9

(a) (b)
Theplots
Figure7.7.The
Figure lg(
plotsofoflg( β))vs.vs.1000/T
1000/Tof
ofTE
TE(a)
(a)and
andFRTE
FRTE (b).
(b).

The apparent activation energy values of neat TE and FRTE composites were obtained
The apparent activation energy values of neat TE and FRTE composites were ob-
by the Flynn–Wall–Ozawa method in the conversion range of 10–60%. The values of
tained by the Flynn–Wall–Ozawa method in the conversion range of 10–60%. The values
conversion 10%, 20%, 30%, 40%, 50% and 60% were used, and the activation energy values
of conversion 10%, 20%, 30%, 40%, 50% and 60% were used, and the activation energy
corresponding to the different conversion are listed in Table 3. It was found that the E of
values corresponding to the different conversion are listed in Table 3. It was found that
neat TE was lower than that of FRTE composites in the conversion range of 10–60%. The
the E of neat TE was lower than that of FRTE composites in the conversion range of 10–
average activation of neat TE and FRTE were 114.9 kJ/mol and 118.2 kJ/mol, respectively.
60%. The average activation of neat TE and FRTE were 114.9 kJ/mol and 118.2 kJ/mol,
respectively.
Table 3. Activation energies of TE and FRTE degradation by Flynn–Wall–Ozawa method.
Table 3. Activation energies of TE and FRTE degradation by Flynn–Wall–Ozawa
E (kJ/mol) method.
a
TE E (kJ/mol) FRTE
a
0.10 TE
114.8 FRTE
117.6
0.10
0.20 114.8
114.8 117.6
117.1
0.30
0.20 114.3
114.8 117.5
117.1
0.40 113.9 118.0
0.30 114.3 117.5
0.50 114.5 118.8
0.40
0.60 113.9
116.9 118.0
120.5
0.50 values
Average 114.5
114.9 118.8
118.2
0.60 116.9 120.5
Average values 114.9 118.2
It can be obtained from the increase in the apparent activation energy of the TE
degradation that the incorporation of flame-retardant PMDA could improve the mainly
It can be obtained from the increase in the apparent activation energy of the TE deg-
thermal stability of neat TE but did not change the degradation mechanism of TE. Therefore,
radation that of
the increase thechar
incorporation of flame-retardant
residue amounts of FRTE wasPMDA couldwhich
important, improve thebeneficial
were mainly ther-
to the
mal stability of neat TE but did not change
formation of a protective layer in combustion.the degradation mechanism of TE. Therefore,
the increase of char residue amounts of FRTE was important, which were beneficial to the
formation of a protective layer in combustion.
4. Conclusions
In summary, a novel silicone flame-retardant PMDA, containing methyl, phenyl and
4. Conclusions
amino groups in the structure, was successfully synthesized. Subsequently, it was incorpo-
ratedIninto
summary, a novel silicone
a commercial thiol–ene flame-retardant
(TE) to obtainPMDA, containing TE
a flame-retardant methyl,
(FRTE)phenyl and
composite.
amino groups in the structure, was successfully synthesized. Subsequently,
The cone calorimeter measurement showed that the incorporation of PMDA improved it was incor-
porated
the flame into a commercial
retardancy of thethiol–ene (TE) to obtain
TE composite a flame-retardant
at concentrations TE (FRTE)
of 5 wt%. Compared compo-with
site. The TE,
the neat conethe calorimeter
PHRR andmeasurement
THR of FRTEshowed that the incorporation
were significantly of PMDA
reduced by 39.4% im-
and 25.4%,
proved the flame
respectively. Theretardancy of the TEand
thermal stability composite at concentrations
degradation mechanism of of5FRTE
wt%. in Compared
a nitrogen
with the neat TE, the PHRR and THR of FRTE were significantly reduced
atmosphere were studied by thermogravimetric analysis. A significant increase in charring by 39.4% and
25.4%, respectively. The thermal stability and degradation mechanism
was observed in the FRTE, which increased by 2% compared with the neat TE. Moreover, of FRTE in a nitro-
gen
the atmosphere were studied
kinetics of thermal by thermogravimetric
degradation were evaluated byanalysis.
KissingerA method
significant
andincrease in
Flynn–Wall–
charring was observed in the FRTE, which increased by 2% compared
Ozawa method. The results showed that the apparent activation energies of the FRTE with the neat TE.
Moreover,
degradation thewere
kinetics of thermal
higher than thosedegradation were
of neat TE. evaluated
However, theby Kissinger method
degradation mechanism and of
Flynn–Wall–Ozawa
the TE matrix did not method.
changeThe by results showed thatofthe
the incorporation apparent activation
a flame-retardant PMDA. energies of
Polymers 2022, 14, 4335 8 of 9

Author Contributions: Conceptualization, H.C., S.Z., R.Z. and J.W.; methodology, J.W. and W.Z.;
validation, W.Z., X.H. and J.W.; formal analysis, J.W. and X.W.; investigation, X.W.; supervision, J.W.
and X.H.; writing—original draft preparation, H.C. and S.Z.; writing—review and editing, W.Z., X.H.
and J.W.; project administration, J.W.; funding acquisition, J.W. All authors have read and agreed to
the published version of the manuscript.
Funding: This work was funded by the National Natural Science Foundation of China (51703099),
Zhejiang Provincial Natural Science Foundation of China (Y20B060020) and Chongben Foundation.
This work was also supported by the Open Fund of Shanghai Key Laboratory of Multiphase Materials
Chemical Engineering.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data used to support the findings of this study are available from
the corresponding author upon request.
Acknowledgments: We gratefully acknowledge the financial support of the above funds and the
researchers of all reports cited in our paper.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Elsheikh, A.; Shanmugan, S.; Muthuramalingam, T.; El-Kassas, A.; Ramesh, B. Recent progresses in wood-plastic composites:
Pre-processing treatments, manufacturing techniques, recyclability and eco-friendly assessment. Clean. Eng. Technol. 2022,
8, 100450. [CrossRef]
2. Kamal, A.; Ashmawy, M.; Shanmugan, S.; Algazzar, A.; Elsheikh, A. Fabrication techniques of polymeric nanocomposites:
A comprehensive review. J. Mech. Eng. Sci. 2021, 236, 4843–4861. [CrossRef]
3. Showaib, E.; Elsheikh, A. Effect of surface preparation on the strength of vibration welded butt joint made from PBT composite.
Polym. Test. 2020, 83, 106319. [CrossRef]
4. Deker, C. Kinetic study and new applications of UV radiation curing. Macromol. Rapid Commun. 2002, 23, 1067–1093. [CrossRef]
5. Yao, H.-Y.; Lin, H.-R.; Sue, G.-P.; Lin, Y.-J. Chitosan-based hydrogels prepared by UV polymerization for wound dressing. Polym.
Polym. Compos. 2019, 27, 155–167. [CrossRef]
6. Qian, J.; Li, Z.; Huang, N.; Lu, Q.; Xia, J. UV-Irradiation Polymerization of Bis-EDOT Methane Derivatives and Their Application
for Br2 Detection. Polymer 2021, 226, 123808. [CrossRef]
7. Shin, J.; Nazarenko, S.; Phillips, J.P.; Hoyle, C.E. Physical and chemical modifications of thiol-ene networks to control activation
energy of enthalpy relaxation. Polymer 2009, 50, 6281–6286. [CrossRef]
8. Kwisnek, L.; Nazarenko, S.; Hoyle, C. Oxygen transport properties of thiol-ene networks. Macromolecules 2009, 42, 7031–7041.
[CrossRef]
9. Hoyle, C.; Bowman, C. Thiol-ene click chemistry. Angew. Chem. Int. Ed. 2010, 49, 1540–1573. [CrossRef]
10. Lee, J.; Lee, Y.; Park, S.; Ha, K. Preparation and Properties of Thiol-ene UV-cured Nanocomposites with Methacrylate-grafted
Cellulose Nanocrystals as Fillers. Polym. Korea 2019, 43, 612–620. [CrossRef]
11. Ma, S.; Wang, Y.; Zhang, H.; Li, Y.; Ou, J.; Wei, Y.; Ye, M. One-step fabrication of cinchona-based hybrid monolithic chiral
stationary phases via photo-initiated thiol-ene polymerization for cLC enantioseparation. Talanta 2019, 198, 432–439. [CrossRef]
[PubMed]
12. Çakmakçı, E.; Mülazim, Y.; Kahraman, M.; Apohan, N. Flame retardant thiol-ene photocured coatings. React. Funct. Polym. 2011,
71, 36–41. [CrossRef]
13. Çakmakçı, E.; Mülazim, Y.; Kahraman, M.; Apohan, N. Preparation and characterization of boron containing thiol-ene photocured.
Prog. Org. Coat. 2012, 75, 28–32. [CrossRef]
14. Wang, W.; Peng, L.; Hsiue, G. Characterization and properties of new silicone-containing epoxy resin. Polymer 2000, 41, 6113–6120.
[CrossRef]
15. Liu, S.; Ye, H.; Zhou, Y.; He, J.; Jiang, Z.; Zhao, J.; Huang, X. Study on flame-retardant mechanism of polycarbonate containing
sulfonate-silsesquioxane-fluoro retardants by TGA and FTIR. Polym. Degrad. Stab. 2006, 91, 1808–1814. [CrossRef]
16. Wang, J.; Xin, Z. Flame retardancy, thermal, rheological and mechanical properties of polycarbonate/polysilsesquioxane system.
J. Appl. Polym. Sci. 2010, 115, 330–337. [CrossRef]
17. Wu, K.; Song, L.; Hu, Y.; Lu, H.; Kandola, B.; Kandare, E. Synthesis and characterization of a functional polyhedral oligomeric
silsesquioxane and its flame retardancy in epoxy resin. Prog. Org. Coat. 2009, 65, 490–497. [CrossRef]
18. Achar, B.; Fohlen, G.; Lokesh, K. Degradation study on the thermally stable nickel phthalocyanine sheet polymer. Polym. Degrad.
Stab. 2003, 80, 427–433. [CrossRef]
19. Achar, B.; Lokesh, K.; Fohlen, G.; Kumar, T. Characterization of cobalt phthalocyanine sheet polymer by gas chromatography
mass spectrometry on its pyrolysis products. React. Funct. Polym. 2005, 63, 63–69. [CrossRef]
Polymers 2022, 14, 4335 9 of 9

20. Ecochard, Y.; Decostanzi, M.; Negrell, C.; Sonnier, R.; Caillol, S. Cardanol and Eugenol Based Flame Retardant Epoxy Monomers
for Thermostable Networks. Molecules 2019, 24, 1818. [CrossRef]
21. Staszko, S.; Półka, M.; Kozikowski, P. Analysis of the Influence of Organophosphorus Compounds and of Aluminium and
Magnesium Hydroxides on Combustion Properties of Epoxy Materials. Energies 2022, 15, 6696. [CrossRef]
22. Kissinger, H. Reaction kinetics in differential thermal analysis. Anal. Chem. 1957, 29, 1702–1706. [CrossRef]
23. Porkodi, P.; Abhilash, J.; Shukla, H. On the structural changes, mechanism and kinetics of stabilization of lignin blended
polyacrylonitrile copolymer fiber. J. Polym. Res. 2022, 29, 436. [CrossRef]
24. Flynn, J. A quick, direct method for the determination of activation energy from thermogravimetric data. J. Polym. Sci. Polym.
Lett. 1966, 4, 323–328. [CrossRef]
25. Flynn, J. Initial kinetic parameters from thermogravimetric rate and conversion data. J. Polym. Sci. Polym. Lett. 1967, 5, 191–196.
[CrossRef]