processes

Article
New Aspects on the Modeling of
Dithiolactone-Mediated Radical Polymerization of
Vinyl Monomers
Anete Joceline Benitez-Carreón 1 , Jesús Guillermo Soriano-Moro 2 , Eduardo Vivaldo-Lima 1,3, * ,
Ramiro Guerrero-Santos 4 and Alexander Penlidis 3
1 Departamento de Ingeniería Química, Facultad de Química, Universidad Nacional Autónoma de México,
Ciudad de Mexico 04510, Mexico; [email protected]
2 Centro de Química, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla (BUAP), Edif. IC8,
Ciudad Universitaria, Puebla 72570, Mexico; [email protected]
3 Institute for Polymer Research (IPR), Department of Chemical Engineering, University of Waterloo,
Waterloo, ON N2L 3G1, Canada; [email protected]
4 Centro de Investigación en Química Aplicada (CIQA), Blvd. Enrique Reyna 140, Saltillo, Coahuila 25140,
Mexico; [email protected]
* Correspondence: [email protected]; Tel.: +52-55-5622-5226




Received: 14 October 2019; Accepted: 7 November 2019; Published: 10 November 2019


Abstract: A kinetic model for the dithiolactone-mediated radical polymerization of vinyl monomers
based on the persistent radical effect and reversible addition (negligible fragmentation) was used
to calculate the polymerization rate and describe molar mass development in the polymerization
of methyl methacrylate at 60 ◦ C, using 2,2-azobisisobutyronitrile (AIBN) as an initiator, as well
as dihydro-5-phenyl-2(3H)-thiophenethione (DTL1) and dihydro-2(3H)-thiophenethione (DTL2) as
controllers. The model was implemented in the PREDICI commercial software. A good agreement
between experimental data and model predictions was obtained.

Keywords: dithiolactones; RAFT polymerization; kinetic modeling; vinyl monomers;

methyl methacrylate

1. Introduction
Reversible deactivation radical polymerization (RDRP) techniques have become important
in the last three decades [1]. They provide versatile routes to synthesize polymers
with tailored architectures [2]. The most studied methodologies which have emerged are
nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible
addition–fragmentation chain-transfer (RAFT) polymerization [3]. However, other RDRP techniques
such as iodine-transfer polymerization (ITP) [4], telluride-mediated polymerization (TERP) [5], and
organostibine-mediated polymerization [5] have also been proposed.
RAFT polymerization is considered one of the most successful RDRP techniques. In RAFT
polymerization, propagating free radical molecule 1 adds to RAFT agent 2 (see Figures 1 and 2),
thus producing intermediate radical 3 (one-arm adduct), which undergoes β-scision, yielding back
the reactants or producing dormant polymer (macro RAFT agent) 4 and radical R· [6]. The main
equilibrium reactions consist of the formation of intermediate radical 6 (two-arm product) and its
fragmentation into free radical 1 and dormant polymer 4 (see Figure 3). In the “intermediate radical
termination” (IRT) model [7], an additional reaction is considered, namely the cross-termination
between free radical 1 and the intermediate radical 6, thus producing a star-shaped polymer (three-arm
dead polymer), as seen in Figure 4 [6]. It is worth mentioning that further investigation has led to the

Processes 2019, 7, 842; doi:10.3390/pr7110842 www.mdpi.com/journal/processes

Processes 2019, 7, 842 2 of 14

Processes 2019, 7, x FOR PEER REVIEW 2 of 15

assumption of side reactions between the three-arm adduct 7 with a propagating radical
Processes 2019, 7, x FOR PEER REVIEW
1 to yield
2 of 15
intermediate
Processesradical
2019,
considered: 7, x 6 and
FOR PEER
reversible a dead
REVIEW
IRT [9]
Processes 2019, 7, x FOR PEER REVIEW polymer
and the [8].
occurrence Variations
of of the IRT
cross-termination model
of the have also
intermediate been
radical2considered:
of
with15
2 of 15
oligomeric
considered: radicals
reversibleonly
IRT(the
[9] IRTO
and model)
the [10].
occurrence Aofreversible reaction
cross-termination between
of the intermediate
intermediate
reversible IRT [9] and the occurrence of cross-termination of the intermediate radical with oligomeric radical
radical with 6
considered:
considered:
and the
oligomeric reversible
reversible
original RAFT
radicals IRT
IRT
only [9]2,
[9]
agent
(the and
and the
the occurrence
occurrence
producing
IRTO model) a ofreversible
of
secondary
[10]. A cross-termination
cross-termination
intermediate of
of the that
the
radical
reaction between intermediate
intermediate
may radical
radical
undergo
intermediate with
with
further
radical 6
radicalsoligomeric
only (theradicals
IRTO onlymodel)(the2,[10].
IRTO A reversible
model) [10]. reactionreaction
A reversible
reversible between intermediate
between radical
intermediate radical 6 6and the
oligomeric
RAFT
and radicals
theprocess,
original has only
also
RAFT (the
been
agent IRTO model)
proposed
producing a[10].
[11]. A
secondary reactionradical
intermediate between thatintermediate
may undergo radical
further 6
originaland
RAFT
and the agent
theprocess,
originalhas
original
2, producing
RAFT
RAFT agent 2, a secondary
producing intermediate
aa secondary
secondary intermediateradical
intermediate radicalthat
radical thatmay
that mayundergo
may undergo further
further RAFT
undergo further
RAFT alsoagent
been 2, producing
proposed [11].
process,RAFT
has also
RAFT been
process,
process, proposed
has
has also been
also [11].
been proposed
proposed [11].
[11].

Figure 1. General chemical structure of a reversible addition–fragmentation chain-transfer (RAFT) agent

(denoted
Figure as AB inchemical
1. General the modeling equations
structure below). addition–fragmentation chain-transfer (RAFT) agent
of a reversible
Figure 1. General
Figure
Figure 1.
(denoted chemical
1. General
General
as AB
chemicalstructure
inchemical structure
the modeling
ofof
structure of
equations abelow).
reversible
aa reversible
reversible addition–fragmentation
addition–fragmentation
addition–fragmentation chain-transfer
chain-transfer
chain-transfer agent(RAFT)
(RAFT) agent
(RAFT)
(denoted
agent (denoted
(denoted asas AB
asAB in the
ABinin modeling
thethe equations
modeling
modeling below).
equations
equations below). below).

Figure 2. Reversible chain transfer to the RAFT agent (pre-equilibrium).

Figure 2. Reversible chain transfer to the RAFT agent (pre-equilibrium).
Figure 2. Reversible
Figure
Figure 2. chain
2. Reversible
Reversible chaintransfer
chain transfer to
transfer theRAFT
the
to the RAFT
RAFT agent
agent
agent (pre-equilibrium).
(pre-equilibrium).
(pre-equilibrium).

Figure 3. Chain equilibration (addition–fragmentation).

Figure 3. Chain equilibration (addition–fragmentation).
Figure 3. Chain equilibration (addition–fragmentation).
Figure 3.
Figure 3. Chain
Chain equilibration
equilibration (addition–fragmentation).
(addition–fragmentation).

Figure 4. Intermediate
Figure 4. Intermediate radical termination
radical termination (IRT).
(IRT).
Figure 4. Intermediate radical termination (IRT).
Dithiolactones are the
Dithiolactones arecyclic counterpart
Figure
the cyclic
Figurecounterpart
4. to dithioester
4. Intermediate
Intermediate radical and
andthiocarbonylthio
radical termination
termination
to dithioester (IRT).
thiocarbonylthio
(IRT). compounds,
compounds, which are
which
used as are
RAFT usedagents.
as RAFT
Dithiolactones However,
agents. as seen
are theHowever,
cyclic in
as Figure
counterpartseen in to5, there5,isthere
Figure
dithioester no
andfragmentation
isthiocarbonylthio
no fragmentation incompounds,
dithiolactone-mediated
in dithiolactone-
which
Dithiolactones
Dithiolactones
mediated
are used free-radical
as RAFT agents.arepolymerizations
are theHowever,
the cyclic counterpart
cyclic counterpart
as (DTLMP),
seen toFigure
to dithioester
dithioester
and the andisthiocarbonylthio
and
additionthiocarbonylthio
noreaction compounds,
compounds,
is reversible which
which
[12,13].
free-radical polymerizations (DTLMP), and thein addition 5, there
reaction isfragmentation
reversible in dithiolactone-
[12,13].
are used
are used
In aasas RAFT agents.
RAFT agents.
previous However,
However,
publication as
fromasour seen in
seengroup,
our Figure
in Figure
we we5,
5, there
there
modeled is no
is the fragmentation
noreaction
fragmentation
DTLMP in dithiolactone-
in dithiolactone-
of styrene using 2,2′- using
In mediated
a previous
mediated
free-radical
free-radical
polymerizations
publication from
polymerizations
(DTLMP),group,
(DTLMP),
and
and
the
the
addition
modeled
addition the is
reaction
reversible
isDTLMP
reversible
[12,13].
of styrene
[12,13].
mediated
In a free-radical
azobisisobutyronitrile
previous polymerizations
(AIBN)
publication as the
from (DTLMP),
initiator
our and
group, and
we the addition
modeled thereaction
γ-phenyl-γ-butyrodithiolactone
DTLMP is reversible
of as
styrene [12,13].
the controller
using 2,2′-
2,20 -azobisisobutyronitrile
In aa previous
previous publication(AIBN)from
publication as our the initiator
our group,
group, we and γ-phenyl-γ-butyrodithiolactone
modeled the DTLMP
DTLMP of of styrene
styrene using 2,2′- as the
[14]. In
azobisisobutyronitrile (AIBN) asfromthe initiator and we modeled the
γ-phenyl-γ-butyrodithiolactone as theusing 2,2′-
controller
controller [14].
azobisisobutyronitrile
azobisisobutyronitrile
[14]. In this contribution, (AIBN)
(AIBN) as the
as the initiator
we address initiator
the DTLMP and of
and γ-phenyl-γ-butyrodithiolactone
γ-phenyl-γ-butyrodithiolactone
methyl methacrylate (MMA) using as the
as thedihydro-5-
controller
controller
[14].
In [14].
thisIn contribution,
phenyl-2(3H)-thiophenethione—whosewe address the
common DTLMP
name is of methyl methacrylate
γ-phenyl-γ-butyrodithiolactone
this contribution, we address the DTLMP of methyl methacrylate (MMA) using dihydro-5- (MMA)
(referred using
InDTL1
In this contribution,
this contribution, we address
we address the
the DTLMPname
DTLMP of methyl
of methyl methacrylate (MMA)
methacrylate (MMA) usingusing dihydro-5-
dihydro-5-
dihydro-5-phenyl-2(3H)-thiophenethione—whose common name is γ-phenyl-γ-butyrodithiolactone
to as in the remainder
phenyl-2(3H)-thiophenethione—whose of our contribution)—and
common is dihydro-2(3H)-thiophenethione—whose
γ-phenyl-γ-butyrodithiolactone (referred
phenyl-2(3H)-thiophenethione—whose common name is γ-phenyl-γ-butyrodithiolactone
γ-phenyl-γ-butyrodithiolactone (referred
(referredphenyl-2(3H)-thiophenethione—whose
common
to
to
toas
asDTL1
as
name
DTL1
DTL1
ininisthe
in
γ-butyrodithiolactone
the
the
remainder
remainderof
remainder of
ofour common
(referred to
ourcontribution)—and
our
name
contribution)—and
contribution)—and
is
as DTL2 indihydro-2(3H)-thiophenethione—whose
the remainder of our contribution)—
dihydro-2(3H)-thiophenethione—whose
dihydro-2(3H)-thiophenethione—whose
(referred
to as DTL1
as controllers, infromthe remainder
both of our and
experimental contribution)—and
mathematical dihydro-2(3H)-thiophenethione—whose
modeling perspectives.
commoncommonname is
common
name is γ-butyrodithiolactone
γ-butyrodithiolactone
name is γ-butyrodithiolactone
γ-butyrodithiolactone
(referred
(referred
(referred toto as DTL2
toasasDTL2
DTL2
in the remainder
inthe
in theremainder
remainder of our contribution)—
of our
of our
our contribution)—as
contribution)—
common
as name
controllers, is
from both experimental and (referred to as
mathematical DTL2 in
modelingthe remainder
perspectives.of contribution)—
controllers,
as from both
as controllers,
controllers, from
from experimental
both and mathematical
both experimental
experimental and mathematical
and mathematical modeling
modelingperspectives.
modeling perspectives.
perspectives.
Processes 2019, 7, 842 3 of 14
Processes 2019, 7, x FOR PEER REVIEW 3 of 15

Figure
Figure 5. Polymerizationscheme
5. Polymerization scheme
forfor dithiolactone-mediated
dithiolactone-mediated (DTLM)
(DTLM) radical
radical polymerization
polymerization of
of vinyl
vinyl monomers.
monomers.
2. Experimental
2. Experimental
As mentioned above, the system studied in this contribution was the polymerization of MMA
usingAs mentioned
AIBN above,
as initiator andthe
DTL1system studied
as well in this
as DTL2 contributionThe
as controllers. waspolymerizations
the polymerization wereofcarried
MMA
using AIBN as initiator
◦ and DTL1 as well as DTL2 as controllers. The polymerizations
out at 333.15 K (60 C) using two molar ratios of DTL1 and DTL2 (monomer:controller:initiator ratios were carried
out
of at 333.15
300:2:1 andK300:4:1)
(60 °C)[13,15].
using two molar ratios of DTL1 and DTL2 (monomer:controller:initiator ratios
of 300:2:1 and 300:4:1) [13,15].
2.1. Polymerization Procedure
2.1. Polymerization Procedure
A stock solution of AIBN in MMA was prepared first, then split into several heavy-wall glass
tubes,Aand stock solution
mixed with of AIBN inamounts
calculated MMA was prepared (DTL1
of controller first, then split into
or DTL2). severalwere
Mixtures heavy-wall
degassed glass
by
tubes,freeze–thaw–pump
three and mixed with calculated amounts
cycles, sealed, andof controller
heated (DTL1
at 333.15 K inoraDTL2). Mixtures
thermostated oil were
bath. degassed
A referenceby
three freeze–thaw–pump cycles, sealed, and heated at 333.15 K in a thermostated oil
experiment was carried out using the original stock solution without the chain transfer agent. Polymers bath. A reference
experiment
were isolatedwas carried out in
by precipitation using the original
methanol. Monomer stock solution was
conversion without the chain determined
gravimetrically transfer agent.
by
Polymers in
duplicate, were isolated
all cases [13].by precipitation in methanol. Monomer conversion was gravimetrically
determined by duplicate, in all cases [13].
2.2. Measurement of Molar Mass Characteristics
2.2. Measurement of Molar Mass Characteristics
Molar mass distributions were determined by size exclusion chromatography (SEC) or gel
Molar chromatography
permeation mass distributions were
(GPC) determined
with by size (HP)
a Hewlett Packard exclusion
modularchromatography
system comprising(SEC)anorauto
gel
permeation
injector, chromatography
a Polymer Laboratories (GPC)
5.0 µm with a Hewlett
bead-size guardPackard
column, (HP)
andmodular
by threesystem comprising
linear PLgel columns an
auto 105
(106, injector,
and 103 a Polymer Laboratories
Å), with differential 5.0 μmindex
refractive bead-size
detectorguard
(HP column,
147 A) and and by three(UV)
ultraviolet linear PLgel
detector.
columns
The eluent (106,
was105 and 103 Å), with
tetrahydrofuran differential
(THF) at a flowrefractive cm3 min
rate of 1index −1 at 313.15
detector (HP 147K.A) Theand ultraviolet
system was
(UV) detector.
calibrated usingThe eluent
narrow was tetrahydrofuran
poly(methyl methacrylate) (THF) at a flow
standards rate of
(ranging 1 cm
from 3 min
620 106 g mol
−1 at×313.15
to 1.52 −1 ).
K. The
system
Data was calibrated
acquisition using narrow
was performed usingpoly(methyl methacrylate)
Polymer Laboratories GPCstandards
software.(ranging from 620 towere
All measurements 1.52
× 10 g mol
obtained
6 ). Data [13].
by duplicate
−1 acquisition was performed using Polymer Laboratories GPC software. All
measurements were obtained by duplicate [13].
3. Modeling
3. Modeling
3.1. Polymerization Scheme
3.1. Polymerization Schemescheme used for our simulations was based on the reaction mechanism
The polymerization
proposed by Soriano-Moro et al. for
The polymerization scheme DTL1
used for [13,15], shown in was
our simulations Figure 5. This
based polymerization
on the scheme
reaction mechanism
corresponded to a RAFT polymerization
proposed by Soriano-Moro without
et al. for DTL1 fragmentation.
[13,15], Its implementation
shown in Figure in the PREDICI
5. This polymerization scheme
corresponded to a RAFT polymerization without fragmentation. Its implementation in the PREDICI
Processes 2019, 7, 842 4 of 14

software package of CiT [16,17], which was the numerical tool to carry out the simulations, is shown in
Table 1. The initiation, propagation and bimolecular radical termination correspond to conventional
free radical polymerization [14,18,19]. The first reversible addition [20], second reversible addition
(which is the reaction between two molecules of intermediate radicals generating a new type of
adduct (see Figure 6)) [13], and reversible cross-termination are reactions due to the presence of
dithiolactone controller molecules, as explained above [13–15]. Also shown in Table 1 are parameter
sources [14,18–23]. It can be observed in Table 1 that our values of K = kadd /k-add for DTL1 and DTL2,
which were in the range of 105 –106 m3 kmol−1 for conventional RAFT agents, were slightly low.

Table 1. Polymerization scheme and kinetic rate constants used.

k (m3 kmol−1 s−1 , Unless

Processes 2019, 7, x FOR PEER REVIEW
Reaction Step Pattern
Otherwise Stated)
DTL1 [Source] DTL2 [Source] 4 of 15
Initiator
I→I• +I• k (s−1 )
d 4 × 10−6 [21] 4 × 10−6 [21]
software package of CiT [16,17], which was the numerical
decomposition tool to carry out the simulations, is shown
First propagation I• +M→P•s=1 ki 833 [18]
in Table 1. The initiation, propagation and bimolecular radical termination 833 [18]
correspond to
Propagation P•s +M→P•s+1 kp 685.9 [22,23] 685.9 [22,23]
conventional free radical polymerization [14,18,19]. The first reversible addition [20], second
P•s +DTL→Ps DTL• kadd 2.3 × 103 [this work] 8.1 ×103 [this work]
reversible addition (which
First reversible is the
Ps DTL →Ps +DTL
• • reaction between two
k−add
molecules of intermediate
−2
2.622 × 10 [this work]
radicals generating
8.6 × 10−2 [this work]
addition
a new type of
Reversible
adduct (see Figure
Ps +Pr DTL →Ps DTLPr
• • 6)) [13], and reversible
krt cross-termination 2
5 ×10 [14] are reactions
5 × 103 [this due
work] to the
presence of dithiolactone
cross-termination controller
Ps DTLPr →Ps +Pr DTL
• molecules,
• as explained
k−rt above [13–15].
−4
2 ×10 [this work] Also shown
2 ×10 [this work] 1 are
−4 in Table
parameter sources [14,18–23].
Irreversible Ps +Pr →D
• •
Its +D
canr be observed in ktdTable 1 that 3.40
our× 10values
7 [22,23] of K =3.40kadd×10
/k7-add for DTL1
[22,23]
termination Ps +Prrange
• • 7 7 [22,23]
and DTL2, which were in the →Ds+r of 105–106 m3 kmol ktc −1 for conventional RAFT agents,
9.78 × 10 [22,23] 9.78 × 10were slightly
Ps DTL• +Pr DTL• →Ps DTLDTLPr kes 2 ×102 [this work] 2 ×102 [this work]
low. Second reversible
addition Ps DTLDTLPr →Ps DTL +Pr DTL
• • k−es 4 ×10−4 [this work] 4 ×10−4 [this work]

Figure 6. Second reversible addition reaction.

Figure 6. Second reversible addition reaction.
3.2. Diffusion-Controlled (DC) Effects
Free-volume theory Table 1.was
Polymerization
used to scheme and kinetic
account rate constants used.
for diffusion-controlled (DC) effects in
(conversion-dependent) kinetic rate constants. kThe expressions
(m3 kmol −1 s−1, used for DC-effects are summarized
2 [14,18]. βi in the expressions
in TableReaction Step Pattern of Table 2 areOtherwise
Unless the free-volume “overlap” parameters
DTL1 [Source] DTL2 [Source] for the
i-th reaction, with i accounting for termination, propagation, Stated) forward and reverse addition (first and
Initiator and
second), decomposition 𝐼𝐼 • +𝐼 •
reversible cross-termination; T and Tg𝑘i are(s−1the
) reaction4 ×temperature
10 [21] and4glass
× 10 transition
[21]
• •
First propagation 𝐼 +𝑀𝑃 𝑘 833 [18] 833 [18]
temperature of component i, respectively; αi is volumetric expansion coefficient for species i; Vi and
Propagation 𝑃• +𝑀𝑃• 𝑘 685.9 [22,23] 685.9 [22,23]
Vt denote the volumes
First reversible of species i
𝑃• +𝐷𝑇𝐿𝑃 𝐷𝑇𝐿•and total volumes,𝑘 respectively; v3f0[this
2.3 × 10 and vf denote
work] fractional
8.1 × 10 free
[this work]
volume addition
at initial conditions and𝑃• •
at +𝐷𝑇𝐿calculation time,
𝑃 𝐷𝑇𝐿 𝑘 respectively. 2.622 ×The free-volume
10−2 [this work] 8.6 ×parameters
10−2 [this work]are
summarized
Reversible in 𝑃• +𝑃
Table 3. As
cross- 𝐷𝑇𝐿• 𝑃 𝐷𝑇𝐿𝑃
mentioned 𝑘
earlier, the simulations were5 × carried 5 × 10the
10 [14] out using PREDICI
[this work]
software termination 𝑃 𝐷𝑇𝐿𝑃 𝑃• +𝑃 𝐷𝑇𝐿•
of CiT, version 11.3.0. 𝑘 2 × 10 [this work] 2 × 10 [this work]
• •
𝑃 +𝑃 𝐷 +𝐷 𝑘 3.40 × 10 [22,23] 3.40 × 10 [22,23]
Irreversible termination
𝑃• +𝑃• 𝐷 𝑘 9.78 × 10 [22,23] 9.78 × 10 [22,23]
Second reversible 𝑃 𝐷𝑇𝐿• +𝑃 𝐷𝑇𝐿• 𝑃 𝐷𝑇𝐿𝐷𝑇𝐿𝑃 𝑘 2 × 10 [this work] 2 × 10 [this work]
addition 𝑃 𝐷𝑇𝐿𝐷𝑇𝐿𝑃 𝑃 𝐷𝑇𝐿• +𝑃 𝐷𝑇𝐿• 𝑘 4 × 10 [this work] 4 × 10 [this work]

3.2. Diffusion-Controlled (DC) Effects

Free-volume theory was used to account for diffusion-controlled (DC) effects in (conversion-
dependent) kinetic rate constants. The expressions used for DC-effects are summarized in Table 2
[14,18]. βi in the expressions of Table 2 are the free-volume “overlap” parameters for the i-th reaction,
with i accounting for termination, propagation, forward and reverse addition (first and second), and
reversible cross-termination; T and Tgi are the reaction temperature and glass transition temperature
of component i, respectively; αi is volumetric expansion coefficient for species i; Vi and Vt denote the
Processes 2019, 7, 842 5 of 14

Table 2. Mathematical expressions for diffusion-controlled (DC)-effects.

β Parameters for DC-Expressions

Reaction Mathematical Expression
[Source]
 
1 1
Propagation kp = kp0 Exp[−βp Vf − Vf0 ] 0.01 [14]
 
0 Exp[−β 1 1 0.01 [14]
kadd = kadd add Vf − Vf0 ]
First reversible addition
k−add =
0.01 [14]
 
0 1 1
k−add Exp[−β−add Vf − Vf0 ]
 
1
0 Exp[−β
krt = krt rt Vf − V1f 0 ] 0.45 [this work]
Reversible cross-termination  
0 Exp[−β 1 1 0.45 [this work]
k−rt = k−rt −rt V f − V f 0 ]
 
0 Exp[−β 1 1 0.45 [14]
ktc = ktc tc V f − V f 0 ]
Irreversible Termination  
0 Exp[−β 1 1 0.45 [14]
ktd = ktd td V f − V f 0 ]
 
0 Exp[−β 1 1 0.55 [this work]
kes = kes es V f − V f 0 ]
Second reversible addition  
0 Exp[−β 1 1 0.55 [this work]
k−es = k−es −es V f − V f 0 ]

N h  i V
0.025 + αi T − T gi V
P i
Fractional Free Volume Vf = t
i=1

Table 3. Other free-volume parameters.

Parameter Value Reference

αMMA (K−1 ), TgMMA (K) 0.001, 143 [24], [25]
αPMMA (K−1 ), TgPMMA (K) 0.0048, 392 [24], [25]
αDTL1 (K−1 , TgDTL1 (K) 0.0001, 173.15 [14], [14]
αDTL2 (K−1 ), TgDTL2 (K) 0.0001, 173.15 This work, this work

3.3. Parameter Estimation Strategy

Literature values were used for kd , ki , kp , ktc and ktd (see Table 1). Given the wide variation range
on reported ktc and ktd values for MMA and the large effect of the ratio ktc /ktd on the evolution of Mn
versus conversion profiles, a careful evaluation (mimicking a sensitivity analysis) of the reported values
was carried out. The best results were obtained with the parameters reported in the Watpoly software
database [22]. Once these parameters were fixed, a more detailed parameter sensitivity analysis was
conducted with the remaining parameters, the ones related to the RDRP behavior of dithiolactones
(kadd , k-add , krt , k-rt , kes , and k-es ). The parameters accounting for DC-effects were assumed to be similar to
the ones estimated for the polymerization of styrene using DTL1 [14] and the same for both controllers
(DTL1 and DTL2). They are summarized in Table 2 (last column).
The overall strategy used in our study is similar to the one used by Gomez-Reguera et al. [26].

4. Results and Discussion

4.1. Polymerization of MMA Using DTL1

The effect of DTL1 concentration on polymerization rate, expressed as conversion versus time,
number average molar mass (Mn ), and molar mass dispersity (Ð), is shown in Figure 7. As expected, it
can be observed in Figure 7 that increasing DTL1 concentration resulted in a slower polymerization
rate, a lower molar mass, and a slightly lower Ð.
Processes 2019, 7, 842 6 of 14
Processes 2019, 7, x FOR PEER REVIEW 6 of 15

1
0.9
0.8
0.7 300:2:1

Conversion
0.6
0.5 Data
300:2:1
0.4
0.3 300:4:1

0.2
Data
0.1
300:4:1
0
0 200 400 600
Time (min)

(a)
140000

120000

100000

80000
Mn

60000

40000

20000

0
0 0.2 0.4 0.6 0.8 1
Conversion
(b)
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
0 0.2 0.4 0.6 0.8 1
Conversion

(c)

Figure
Figure 7. 7. Comparison
Comparison of ofmodel
model predictions
predictions andand
experimental data of (a)
experimental datamonomer
of (a) conversion
monomerversus
conversion
time, (b) number average molar mass versus conversion, and (c) Ð versus conversion. [methyl
versus time, (b) number average molar mass versus conversion, and (c) Ð versus conversion.
methacrylate (MMA)]:[γ-phenyl-γ-butyrodithiolactone (DTL1)]:[2,2-azobisisobutyronitrile
[methyl(AIBN)]=300:2:1
methacrylatefor(MMA)]:[γ-phenyl-γ-butyrodithiolactone
EXP 1 and 300:4:1 for EXP 2.
(DTL1)]:[2,2-azobisisobutyronitrile
(AIBN)]=300:2:1 for EXP 1 and 300:4:1 for EXP 2.

Overall, a fair agreement can be observed in Figure 7 between the calculated and experimental
profiles, with some deviations. The evolution of polymerization rate and molecular weight development
were captured well by the model in the case of 300:2:1, but significant deviations were observed for
both profiles in the case of 300:4:1. Several attempts to improve the agreement between calculated
and experimental profiles of Mn versus conversion for the case of 300:4:1 by fine-tuning some of the
kinetic rate constants or DC effect parameters were made. If the agreement was improved, the changes
Processes 2019, 7, 842 7 of 14

resulted in the worsening of the agreement for the conversion versus time profiles, as well as the
obtainment of a very poor performance for the case of 300:2:1. This is not uncommon in modelling
attempts when multi-response data points are used with the same set of parameters. Therefore, the
behavior of Mn after 20% monomer conversion observed in the case of 300:4:1 suggests either a high(er)
experimental error occurring in this case, or, more likely, the presence of side reactions not considered
in the polymerization scheme when the controller content was high. The deviations are also evident in
Figure 7 for the case of Ð versus conversion. Again, this points towards the direction of side reactions
affecting the data—reactions which are unaccounted for in the polymerization mechanism and, hence,
in the subsequent mathematical model. It is also possible that the parameters associated to DC effects
may have become conversion dependent [26]. A similar overall performance was observed in the case
of polymerization of styrene using DTL1 [13,14].
A comparison of calculated and experimental full molar mass distributions (MMDs) for the cases
using DTL1 is shown in Figure 8. The calculated MMDs of Figure 8 are narrower than the experimental
ones. This result agrees with the Ð versus conversion profiles of Figure 7, where calculated Ð values
are lower than the experimental ones. However, the time evolution of the MMDs and the effect
of controller on both Mn and the spread of the MMD were well captured by the model. As stated
earlier, the disagreement between calculated and experimental profiles of Ð versus conversion and
time evolution of the MMDs may be attributed to chain transfer side reactions [21]. Several possible
Processes 2019,and
alternatives 7, x changes
FOR PEERin
REVIEW 8 of 15
the polymerization scheme, including reversible fragmentation (full RAFT
case) and other side reactions, were indeed simulated in this study, but no significant improvement
incomplete,
was obtained. pointing again towards other side reactions in the mechanism, as postulated above
during the discussion of the experimental results of Figures 7 and 8.

(a)
(b)

Figure 8. Evolution
Figure of molar-mass
8. Evolution distributions
of molar-mass distributionsfor
forpolymerizations
polymerizations using DTL1 (experimental
using DTL1 (experimentalandand
simulated): (a) 300:2:1 and (b) 300:4:1. Labels: “1” = 30, ”2” = 60, ”3” = 90, ”4” = 120, ”5” = 150, “6” =
simulated): (a) 300:2:1 and (b) 300:4:1. Labels: “1” = 30, ”2” = 60, ”3” = 90, ”4” = 120, ”5” = 150, “6” = 180
180 min. min.

As mentioned earlier, no measurements of polymer radical concentration versus time were

obtained for the case of the DTLM polymerization of MMA. However, calculated profiles were
generated, and the ranges are like those of Figure 9. Figure 10 shows calculated profiles of overall
polymer radical concentration (black solid line) and polymer radicals excluding the “dormant”
population (PsDTL•, red solid line). It can again be observed that most of the polymer radical
population is made out of dormant polymer PsDTL•, which allows the polymerization to be
Processes 2019, 7, 842 8 of 14

In our previous investigation on the polymerization of styrene using DTL1 or benzyl

dithiopropianate (BDP), overall radical concentrations were measured using electro-spin resonance
(ESR) spectroscopy. Overall radical concentrations in the order of 10−7 –10−6 kmol m−3 were
obtained [13,15]. Though the model used included the calculation of concentrations of all the
species involved in the polymerization scheme, no comparison between calculated and experimental
profiles of overall radical concentration versus time was presented. Moad et al. [27] pointed out that
the reversible addition mechanism for the DTLMP of vinyl monomers proposed herein (see Figure 5)
seems unlikely since, for control, most of the propagating species would need to be present at the
dormant state (polymer product in the forward direction of the reversible addition reaction of Figure 5,
or species Ps DTL• in Table 1). They added that ESR experiments (triangles in Figure 9) showed
that a high concentration of radicals was not present during polymerization, thus implying that the
mechanism would suggest that the final product should also have the Ps DTL• structure. In order to
gain more insight regarding this issue, we carried out simulations of overall radical concentration
versus time for both styrene and MMA DTLMPs, using DTL1 for styrene and MMA, as well as DTL2
for MMA.Processes
The results using DTL1 are shown in Figures 9 and 10. (Results using DTL2 are
2019, 7, x FOR PEER REVIEW
shown in
9 of 15
Section 4.2).
Processes 2019, 7, x FOR PEER REVIEW 9 of 15

0.1000000000
Polymer Radical Concentration, kmol/m3 3

0.1000000000
Polymer Radical Concentration, kmol/m

0.0100000000
0.0100000000
0.0010000000
0.0010000000
0.0001000000
0.0001000000
0.0000100000
0.0000100000
0.0000010000
0.0000010000
0.0000001000
0.0000001000
0.0000000100
0.0000000100
0.0000000010
0.0000000010
0.0000000001
0.0000000001 0 20 40 60 80 100 120 140
0 20 40 60 80 100 120 140
Time (min)
Time (min)

Comparison
Figure 9. Figure of experimental
9. Comparison of experimental [13,15]
[13,15]and and calculated profiles
calculated profiles of polymer
of polymer radicalradical concentration
concentration
Figure
versus9. Comparison of experimental [13,15] and calculated profiles of polymer radicalofconcentration
versus time fortime
the for the dithiolactone-mediated
dithiolactone-mediated free-radical
free-radical polymerizations
polymerizations (DTLMP)
(DTLMP) styrene using using
of styrene
versus
DTL1:time for polymer
overall the dithiolactone-mediated free-radical
radical (blue solid line); polymerpolymerizations (DTLMP)
radicals excluding PsDTLof styrene
• (red using
solid line);
DTL1: overall polymer radical (blue •
DTL1: overall
experimental polymer radical
data (green (bluesolid
triangles). solid line); polymer
line); polymer radicals
radicals
Monomer:controller:initiator:
excluding P
excluding • s DTL (red solid line);
300:2:1. PsDTL (red solid line);
experimental data (green
experimental triangles).
data (green Monomer:controller:initiator:
triangles). Monomer:controller:initiator: 300:2:1. 300:2:1.

0.0100000000
Polymer Radical Concentration, kmol/m3 3

0.0100000000
Polymer Radical Concentration, kmol/m

0.0010000000
0.0010000000
0.0001000000
0.0001000000
0.0000100000
0.0000100000
0.0000010000
0.0000010000
0.0000001000
0.0000001000
0.0000000100
0.0000000100
0.0000000010
0.0000000010
0.0000000001
0.0000000001 0 25 50 75 100 125 150
0 25 50 75 100 125 150
Time (min)
Time (min)
Figure 10. Calculated profiles of polymer radical concentration in the free radical polymerization of
Figure 10. Calculated profiles of polymer radical concentration in the free radical polymerization of
MMA using
FigureDTL1: overall profiles
polymer polymer
radicalsradical
(blackconcentration
solid line) and polymer radicals excludingof dormant
MMA10. Calculated
using DTL1: overall ofpolymer radicals in the
(black solid line) freepolymer
and radical polymerization
radicals excluding
polymerMMA
Pdormant•
s DTL (red
using solid
DTL1:
polymer line).
Psoverall
DTL polymer
• (red radicals (black solid line) and polymer radicals excluding
solid line).
dormant polymer PsDTL• (red solid line).
4.2. Polymerization of MMA Using DTL2
4.2. Polymerization of MMA Using DTL2
The effect of controller concentration on the polymerization rate and molar mass development for
The effect of controller
the polymerization of MMAconcentration
using DTL2 wason the
alsopolymerization rate
addressed. It can beand molar in
observed mass development
Figure for
11 (upper plot)
the polymerization
that the agreementofbetween
MMA using DTL2 wasand
the calculated also experimental
addressed. It can be observed
profiles in Figure
of conversion 11 (upper
versus time isplot)
very
that the agreement between the calculated and experimental profiles of conversion versus time is very
Processes 2019, 7, 842 9 of 14

It can be observed in Figure 9 that the predicted overall concentration of polymer radicals (blue
solid line, which includes “dormant” polymer Ps DTL• ) exceeded by almost four orders of magnitude
the experimental profile. It can also be observed in that figure that the calculated concentration of
polymer radicals excluding Ps DTL• was one order of magnitude lower than the experimental profile of
the overall polymer radical concentration. This result indicates that the level of control experimentally
obtained would require a much higher content of dormant polymer Ps DTL• , as pointed out by Moad
et al. [27]; this suggests that our proposed polymerization scheme may be incomplete, pointing again
towards other side reactions in the mechanism, as postulated above during the discussion of the
experimental results of Figures 7 and 8.
As mentioned earlier, no measurements of polymer radical concentration versus time were obtained
for the case of the DTLM polymerization of MMA. However, calculated profiles were generated, and
the ranges are like those of Figure 9. Figure 10 shows calculated profiles of overall polymer radical
concentration (black solid line) and polymer radicals excluding the “dormant” population (Ps DTL• ,
red solid line). It can again be observed that most of the polymer radical population is made out of
dormant polymer Ps DTL• , which allows the polymerization to be controlled.

4.2. Polymerization of MMA Using DTL2

The effect of controller concentration on the polymerization rate and molar mass development for
the polymerization of MMA using DTL2 was also addressed. It can be observed in Figure 11 (upper
plot) that the agreement between the calculated and experimental profiles of conversion versus time is
very good for the case of 300:2:1, but large deviations were observed for the case of 300:4:1. It is worth
noting that the experimental profile corresponding to a higher RAFT content (grey triangles) resulted
in higher conversions than the case of 300:2:1, which was contrary to the expected performance. The
calculated profiles, however, showed the correct trend with polymerization rate decreasing as RAFT
content increased. This result suggests that our experimental profile of conversion versus time for
the case of 300:4:1 may have been in error. The agreement between the experimental and calculated
profiles of Mn versus conversion, on the other hand, is very good for both RAFT concentration levels
(see middle plot of Figure 11). It is interesting to notice that the predicted profile of Ð versus conversion
for the case of 300:4:1 also agrees very well with the experimental one, as observed in the bottom plot
of Figure 11. The agreement between the calculated and experimental profiles of Ð versus conversion
for the case of 300:2:1, on the other hand, is again poor, as with DTL1.
The polymerization of MMA using AIBN and DTL1 or DTL2 controllers showed hybrid behavior
between RDRP and conventional chain transfer radical polymerization. This hybrid behavior has
also been observed in the RAFT polymerization of MMA using cumyl phenyldithioacetate [20]. This
hybrid behavior strongly depends on temperature; at temperatures below 45 ◦ C, the conventional
character dominates, whereas controlled behavior dominates at higher temperatures [20].
The comparison of calculated and experimental MMDs shown in Figure 12 confirms the information
provided by the middle and bottom plots of Figure 11. It can be observed that the calculated MMDs
for the case of 300:2:1 were narrower than the experimental ones. In the case of system 300:4:1, the
agreement between the calculated and experimental MMDs is very good, except for the experimental
MMD at very low conversions, which was much broader, verifying a dominant conventional chain
transfer behavior in that case, as alluded to above.
versus conversion, on the other hand, is very good for both RAFT concentration levels (see middle plot of
Figure 11). It is interesting to notice that the predicted profile of Ð versus conversion for the case of 300:4:1
also agrees very well with the experimental one, as observed in the bottom plot of Figure 11. The
agreement between the calculated and experimental profiles of Ð versus conversion for the case of 300:2:1,
on the other
Processes hand,
2019, 7, 842 is again poor, as with DTL1. 10 of 14

0.8
300:2:1

Conversion
0.6 Data
0.4 300:2:1
300:4:1
0.2 Data
0 300:4:1
0 200 400 600
Time (min)

(a)

140000
120000
100000
80000
Mn

60000
40000
20000
0
0 0.2 0.4 0.6 0.8 1
Conversion

(b)

3
Ɖ

0
0 0.2 0.4 0.6 0.8 1
Conversion

(c)
Figure 11. Comparison
Comparison of
of model
model predictions
predictions and
and experimental
experimental data for (a) monomer conversion
versus time, (b) number average molar mass versus conversion,
conversion, and
and (c)
(c) Ð
Ð versus
versus conversion.
conversion.
(DTL2)]:[AIBN] =
[MMA]:[dihydro-2(3)-thiophenethione (DTL2)]:[AIBN] = 300:2:1 for EXP 1 and 300:4:1 for EXP 2.

Finally, the calculated profiles of overall polymer radical concentration and concentration of
dormant polymer (Ps DTL• ) versus time for the case of DTLM polymerization of MMA using DTL2
are shown in Figure 13. As in the case using DTL1 earlier, it can be observed that large amounts of
dormant polymer were required to obtain adequate control.
Processes 2019, 7, x FOR PEER REVIEW 12 of 15
Processes 2019, 7, 842 11 of 14
Processes 2019, 7, x FOR PEER REVIEW 12 of 15

(a) (b)

(a) (b)
Figure
Figure12.
12.Evolution
Evolutionofofthe
themolar-mass
molar-massdistributions
distributionswith
withDTL2
DTL2(experimental
(experimentalshown
shownatatthe
thetop
topand
and
simulated
simulated at the bottom): (a) 300:2:1 and (b) 300:4:1. Labels: “1” = 40, “2” = 60, “3” = 90, “4” = 120,“5”
at the bottom): (a) 300:2:1 and (b) 300:4:1. Labels: “1” = 40, “2” = 60, “3” = 90, “4” = 120, “5”
Figure
==150, “6”12.
= Evolution
180 min.
150, “6” = 180 min. of the molar-mass distributions with DTL2 (experimental shown at the top and
simulated at the bottom): (a) 300:2:1 and (b) 300:4:1. Labels: “1” = 40, “2” = 60, “3” = 90, “4” = 120, “5”
= 150, “6” = 180 min.
0.010000000
Polymer Radical Concentration kmol/m3

0.001000000
0.010000000
Polymer Radical Concentration kmol/m3

0.000100000
0.001000000

0.000010000
0.000100000

0.000001000
0.000010000

0.000000100
0.000001000

0.000000010
0.000000100

0.000000001
0.000000010
0 20 40 60 80 100 120 140 160
0.000000001 Time (min)
0 20 40 60 80 100 120 140 160
Figure 13. Calculated profiles of polymer radical concentration in the free radical polymerization of
Time (min)
MMA using DTL2: overall polymer radicals (black solid line) and polymer radicals excluding dormant
Figure 13. Calculated profiles of polymer radical concentration in the free radical polymerization of
polymer Ps DTL• (red solid line).
MMA using DTL2: overall polymer radicals (black solid line) and polymer radicals excluding
Figure polymer
dormant 13. Calculated
PsDTLprofiles of polymer
• (red solid line). radical concentration in the free radical polymerization of
MMA using DTL2: overall polymer radicals (black solid line) and polymer radicals excluding
dormant polymer PsDTL• (red solid line).
Processes 2019, 7, 842 12 of 14

4.3. Some Thoughts on Future Research Steps

Masoumi et al. [6] used a sequential Bayesian Monte Carlo model discrimination (SBMCMD)
method to discriminate between two rival RAFT models, the so-called slow-fragmentation (SF)
method [28] and one type of IRT model [29]). They found that if one of the two competing models
represents the ‘real’ mechanism behind the RAFT process, the SBMCMD framework can identify
the correct model by analyzing the data from the most informative experiments designed by the
model discrimination steps. However, for the system studied in that paper, if the ‘real’ model was
not known beforehand, the method was not able to discriminate between the SF and IRT models,
based on polymerization rate and molar mass development data (conversion versus time and molar
mass averages versus conversion experimental profiles). The bottom-line conclusion is that additional
independent experimental information (e.g., concentrations of intermediate products) is needed to get
more conclusive results.
As stated in Section 4.1, we carried out additional simulations under different mechanistic
variations, including trials using the full RAFT model (the inclusion of fragmentation), but no
significantly better results were obtained. More comprehensive results in that direction will be
presented by our group in future contributions.

5. Conclusions
The free radical polymerization of MMA in the presence of AIBN and DTL1 or DTL2 at 333.15 K was
studied experimentally and modeled using a polymerization scheme where only reversible addition was
considered (fragmentation neglected). The agreement between the experimental and modeling profiles
of conversion versus time, average molar mass and full MMDs can range from fair to very-good. Our
results complement our previous study on the polymerization of styrene using AIBN and DTL1.
Though the polymerization scheme based on reversible addition only seems to be adequate to
describe the overall performance of dithiolactone-mediated free radical polymerizations, described
typically by polymerization rate and average molar mass development, the fact that the global
description of the system, considering a wide range of experimental conditions and independent
responses was difficult to obtain by using a single set of model parameters, suggests that the proposed
polymerization scheme may be incomplete.
Our modeling results suggest that high concentrations of a dormant polymer (Ps DTL• ) are
required to provide adequate control of the polymerization. This result further suggests that the
polymerization scheme may be incomplete. This is an issue that requires further experimental and
mechanistic considerations in the area of DTLMP.

Author Contributions: A.J.B.-C. performed all the simulations and parameter estimation procedure, guided by
E.V.-L. and A.P., R.G.-S. and J.G.S.-M. conceived the experimental research. J.G.S.-M. conducted all experiments
and characterization. E.V.-L. and R.G.-S. provided technical direction to the project. A.J.B.-C. wrote the paper with
feedback from J.G.S.-M., while E.V.-L. and A.P. revised the different intermediate versions until the final document.
Funding: This research was funded by: (a) Consejo Nacional de Ciencia y Tecnología (CONACYT, México), MEng
scholarship granted to A.J.B.-C.; (b) DGAPA-UNAM, Projects PAPIIT IG100718, IV100119, and PASPA sabbatical
support to E.V.-L. at the University of Waterloo, in Ontario, Canada; (c) Facultad de Química-UNAM, research
funds granted to E.V.-L. (PAIP 5000–9078); (d) VIEP-BUAP, research funds granted to J.G.S.-M. and (e) Natural
Sciences and Engineering Research Council (NSERC) of Canada.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Jenkins, A.D.; Jones, R.G.; Moad, G. Terminology for reversible-deactivation radical polymerization previously
called “controlled” radical or “living” radical polymerization (IUPAC Recommendations 2010). Pure Appl.
Chem. 2009, 82, 483–491. [CrossRef]
2. Luo, Y.D.; Chiu, W.Y. Synthesis and kinetic analysis of DPE controlled radical polymerization of MMA. J.
Polym. Sci. Polym. Chem. 2009, 47, 6789–6800. [CrossRef]
Processes 2019, 7, 842 13 of 14

3. Vivaldo-Lima, E.; Jaramillo-Soto, G.; Penlidis, A. Nitroxide-Mediated Polymerization (NMP). In Encyclopedia

of Polymer Science and Technology, 4th ed.; Mark, H.F., Ed.; John Wiley & Sons: New York, NY, USA, 2016;
pp. 1–48.
4. Kim, K.; Kim, Y.; Ko, N.R.; Choe, S. Effect of molecular weight on the surface morphology of crosslinked
polymer particles in the RITP-dispersion polymerization. Polymer 2011, 52, 5439–5444. [CrossRef]
5. Yamago, S. Development of organotellurium-mediated and organostibine-mediated living radical
polymerization reactions. J. Polym. Sci. Part A Polym. Chem. 2016, 44, 1–12. [CrossRef]
6. Masoumi, S.; Duever, T.A.; Penlidis, A.; Azimi, R.; López-Domínguez, P.; Vivaldo-Lima, E. Model
discrimination between RAFT polymerization models using sequential Bayesian methodology. Macromol.
Theory Simul. 2018, 27, 1800016. [CrossRef]
7. Monteiro, M.J.; de Brouwer, H. Intermediate Radical Termination as the Mechanism for Retardation in
Reversible Addition-Fragmentation Chain Transfer Polymerization. Macromolecules 2001, 34, 349–352.
[CrossRef]
8. Buback, M.; Vana, P. Mechanism of Dithiobenzoate-Mediated RAFT polymerization: A missing reaction
Step. Macromol. Rapid Commun. 2006, 27, 1299. [CrossRef]
9. Barner-Kowollik, C.; Buback, M.; Charleux, B.; Coote, M.L.; Drache, M.; Fukuda, T.; Goto, A.; Klumperman, B.;
Lowe, A.B.; Mcleary, J.B.; et al. Mechanism and Kinetics of Dithiobenzoate-Mediated RAFT Polymerization.
I. The Current Situation. J. Polym. Sci. Part A Polym. Chem. 2006, 44, 5809–5831. [CrossRef]
10. Konkolewicz, D.; Hawkett, B.S.; Gray-Weale, A.; Perrier, S. RAFT Polymerization Kinetics: Combination of
Apparently Conflicting Models. Macromolecules 2008, 41, 6400–6412. [CrossRef]
11. Li, C.; He, J.; Liu, Y.; Zhou, Y.; Yang, Y. Probing the RAFT Process Using a Model Reaction between
Alkoxyamine and Dithioester. Aust. J. Chem. 2012, 65, 1077–1089. [CrossRef]
12. Inuit, T.; Yamanishi, K.; Sato, E.; Matsumoto, A. Organotellurium-Mediated Living Radical Polymerization
(TERP) of Acrylates Using Ditelluride Compounds and Binary Azo Initiators for the Synthesis of
High-Performance Adhesive Block Copolymers for On-Demand Dismantlable Adhesion. Macromolecules
2013, 46, 8111–8120. [CrossRef]
13. Soriano-Moro, J.G.; Rico-Valverde, J.C.; Enriquez-Mendrano, F.J.; Maldonado-Textle, H.; Vivaldo-Lima, E.;
Acosta-Ortiz, R.; Guerrero-Santos, R. Toward a Living Radical Polymerization of Styrene by Using
Dithiolactone as a New Type of Mediating Agent. Macromol. Rapid Commun. 2008, 29, 80–85. [CrossRef]
14. Soriano-Moro, J.G.; Jaramillo-Soto, G.; Guerrero-Santos, R.; Vivaldo-Lima, E. Kinetics and Molecular Weight
Development of Dithiolactone-Mediated Radical Polymerization of Styrene. Macromol. React. Eng. 2009, 3,
178–184. [CrossRef]
15. Soriano-Moro, J.G. Síntesis y Caracterización de Ditiolactonas y su Empleo Como Agentes de Transferencia
en la Polimerización RAFT. Ph.D. Thesis, Programa de Doctorado en Tecnología de Polímeros, CIQA, Saltillo,
México, February 2008.
16. Wulkow, M. Computer Aided Modeling of Polymer Reaction Engineering-The Status of Predici, 1-Simulation.
Macromol. React. Eng. 2008, 2, 461–494. [CrossRef]
17. Hungenberg, K.D.; Wulkow, M. Modeling and Simulation in Polymer Reaction Engineering: A Modular Approach;
Wiley-VCH: Weinheim, Germany, 2018; pp. 92, 256.
18. Beurmann, S.; Buback, M. Rate coefficients of free-radical polymerization deduced from pulsed laser
experiments. Prog. Polym. Sci. 2002, 27, 191–254. [CrossRef]
19. Pallares, J.; Jaramillo-Soto, G.; Flores-Cataño, C.; Vivaldo Lima, E.; Lona, L.M.F.; Penlidis, A. A Comparison
of Reaction Mechanisms for Reversible Addition-Fragmentation Chain Transfer Polymerization Using
Modeling Tools. J. Macromol. Sci. A Pure Appl. Chem. 2006, 43, 1293. [CrossRef]
20. Barner-Kowollik, C.; Quinn, J.F.; Nguyen, T.L.U.; Heuts, J.P.A.; Davis, T.P. Kinetic investigations of
reversible addition fragmentation chain transfer polymerizations: Cumyl phenyldithioacetate mediated
homopolymerizations of styrene and methyl methacrylate. Macromolecules 2001, 34, 7849–7857. [CrossRef]
21. Jaramillo-Soto, G.; Castellanos-Cardenas, M.L.; García-Moran, P.; Vivaldo-Lima, E.; Luna-Barcenas, G.;
Pendilis, A. Simulation of Reversible Addition-Fragmentation Chain Transfer (RAFT) Dispersion
Polymerization in Supercritical Carbon Dioxide. Macromol. Theory Simul. 2008, 17, 280–289. [CrossRef]
22. Jung, W. Mathematical Modeling of Free-Radical Six-Component Bulk and Solution Polymerization. Master’s
Thesis, Department of Chemical Engineering, University of Waterloo, Waterloo, ON, Canada, 2008.
Processes 2019, 7, 842 14 of 14

23. Gao, J.; Penlidis, A. A Comprehensive Simulator Database Package for Reviewing Free-Radical
Copolymerizations. J. Macromol. Sci. Part C Polym. Rev. 1998, 38, 651–780. [CrossRef]
24. Vivaldo-Lima, E.; García-Pérez, R.; Celedón-Briones, O.J. Modeling of the Free-Radical Copolymerization
Kinetics with Crosslinking of Methyl Methacrylate/Ethylene Glycol Dimethacrylate Up to High Conversions
and Considering Thermal Effects. Evista Sociedad Química México 2003, 47, 22–33.
25. Faldi, A.; Tirrell, M.; Lodge, T.P.; von Meerwall, E. Monomer Diffusion and the Kinetics of Methyl Methacrylate
Radical Polymerization at Intermediate to High Conversion. Macromolecules 1994, 27, 4184–4192. [CrossRef]
26. Gómez-Reguera, J.A.; Vivaldo-Lima, E.; Gabriel, V.A.; Dubé, M.A. Modeling of the Free Radical
Copolymerization Kinetics of n-Butyl Acrylate, Methyl Methacrylate and 2-ethylhexyl Acrylate Using
PREDICI. Processes 2019, 7, 395. [CrossRef]
27. Moad, G.; Rizzardo, E.; Thang, S.H. Living Radical Polymerization by the RAFT Process—A Second Update.
Aust. J. Chem. 2009, 62, 1402–1472. [CrossRef]
28. Barner-Kowollik, C.; Quinn, J.F.; Morsley, D.R.; Davis, T.P. Modeling the reversible addition–fragmentation
chain transfer process in cumyl dithiobenzoate-mediated styrene homopolymerizations: Assessing rate
coefficients for the addition–fragmentation equilibrium. J. Polym. Sci. Part A Polym. Chem. 2001, 39,
1353–1365. [CrossRef]
29. Wang, A.R.; Zhu, S. Modeling the reversible addition–fragmentation transfer polymerization process. J. Polym.
Sci. Part A Polym. Chem. 2003, 41, 1553–1566. [CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).