Polymer 106 (2016) 275e284

Contents lists available at ScienceDirect

Polymer
journal homepage: www.elsevier.com/locate/polymer

Surfactant-free poly(vinylidene chloride) latexes via one-pot RAFT-

mediated aqueous polymerization
Emilie Velasquez a, b, Jutta Rieger b, François Stoffelbach b, Franck D'Agosto a, **,
Muriel Lansalot a, *, Pierre-Emmanuel Dufils c, Je
ro^ me Vinas d
a
Universit

e de Lyon, Univ Lyon 1, CPE Lyon, CNRS, UMR 5265, C2P2 (Chemistry, Catalysis, Polymers and Processes), Team LCPP, Bat 308F, 43 Bd du 11
Novembre 1918, 69616 Villeurbanne, France
b
UPMC Univ. Paris 6, Sorbonne Universit
eculaire, Team «Chimie des Polym
es and CNRS, Institut Parisien de Chimie Mol
eres» (LCP), 4, Place Jussieu, 75005
Paris, France
c
SOLVAY, High Barrier Polymers, Avenue de la R
epublique, F-39500 Tavaux, France
d
SOLVAY, High Barrier Polymers, Rue de Ransbeek 310, B-1120 Brussels, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: Water-soluble polymers obtained by reversible addition-fragmentation chain transfer (RAFT) polymer-
Received 22 June 2016 ization were used for the production of surfactant-free poly(vinylidene chloride) (PVDC)-based latexes in
Received in revised form a one-pot/two-step process that was exclusively conducted in water. In the first step, the hydrophilic
22 August 2016
macromolecular RAFT (macroRAFT) agent (i.e. poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA) or
Accepted 24 August 2016
Available online 27 August 2016
poly(sodium 4-styrenesulfonate) (PSSNa)) was synthesized in water using a trithiocarbonate RAFT agent,
4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA). The macroRAFT agent was then directly uti-
lized as reactive stabilizer for the aqueous emulsion copolymerization of vinylidene chloride (VDC) and
Keywords:
RAFT
methyl acrylate (MA) inspired by a polymerization-induced self-assembly (PISA) process. The developed
Emulsion polymerization recipes employed a very low amount of macroRAFT agent compared to the hydrophobic monomers
Surfactant-free (typically less than 2 wt%) and amphiphilic block copolymers of PAA-b-P(VDC-co-MA), PMAA-b-P(VDC-
Vinylidene chloride co-MA) or PSSNa-b-P(VDC-co-MA) were thus produced in situ, providing stabilization to the P(VDC-co-
MA) particles. Stable, surfactant-free latexes were successfully obtained in each case with solids content
up to 40 wt%. Surface tension measurements performed on the final dispersions showed that the amount
of residual macroRAFT agent in water was negligible demonstrating that this strategy indeed gave rise to
particles stabilized by covalently-anchored hydrophilic polymers. The PSSNa macroRAFT agents proved
to be particularly interesting candidates achieving stable latexes of less than 100 nm leading to the
formation of transparent films which did not whiten after being immersed in water.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Low molar mass surfactants are essential to the stabilization of
organic latexes. However, they can have detrimental effects on the
latex stability when frozen or subjected to high shear. They can also
negatively impact the properties of the resulting films when
exposed to water or high humidity. This sensitivity to water is
mostly affected by the location of the surfactant in the film, which
can evolve with time [1e3]. Surfactants can migrate toward the
* Corresponding author.
** Corresponding author.
E-mail addresses: franck.dagosto@univ-lyon1.fr (F. D'Agosto), muriel.lansalot@
univ-lyon1.fr (M. Lansalot).
film-air and the film-substrate interfaces. In some systems, they can
also be pushed away from the particle boundaries and surfactant
aggregates form, trapped within the film. If swollen with water,
these hydrophilic pockets will display a refractive index lower than
that of the polymer, leading to light scattering [4,5]. The film will
thus become cloudy, or even white (water whitening effect). On the
other hand, if strongly adsorbed on the particle surface, surfactants
will be trapped along particles boundaries, likely creating hydro-
philic pathways in the film. The permeability to gases and water
vapor will be adversely affected. All these effects (water whitening
and increased permeability) can be real issues for polymer mate-
rials such as poly(vinylidene chloride) (PVDC), widely used in the
pharmaceutical and food packaging industry. Indeed, PVDC is a
specialty polymer well known for its excellent barrier properties,

http://dx.doi.org/10.1016/j.polymer.2016.08.083
0032-3861/© 2016 Elsevier Ltd. All rights reserved.
276 E. Velasquez et al. / Polymer 106 (2016) 275e284
notably towards water vapor and oxygen [6e8]. Highly crystalline
PVDC homopolymer is however hardly processable and only co-
polymers are commercially important. Vinylidene chloride (VDC) is
thus usually copolymerized with monomers like methyl acrylate,
vinyl chloride or acrylonitrile, by free radical suspension or emul-
sion polymerization.
Over the last 20e30 years, different synthetic strategies have
been proposed to avoid the use of molecular surfactants, one of
them being the utilization of reactive surfactants (in most cases
macromolecular) that will be covalently linked to the particles
during the polymerization [9]. In that respect, the surfactant must
carry a group able to participate to one of the key-steps of the free
radical polymerization process: initiation (inisurf), propagation
(surfmer), transfer (transurf). Recently, an original strategy
combining emulsion polymerization and reversible deactivation
radical polymerization (RDRP) has been developed to produce
surfactant-free latexes. The process requires the synthesis by RDRP
of hydrophilic polymer chains followed by their chain extension
with a hydrophobic monomer in water leading to the formation of
amphiphilic block copolymers. This strategy, coined
polymerization-induced self-assembly (PISA) [10e12], has been
successfully implemented using water-soluble polymers notably
obtained by reversible addition-fragmentation chain transfer
(RAFT) or nitroxide-mediated polymerization (NMP). The imple-
mentation of the PISA technique in a one-pot/two-step process has
further improved the attractiveness of this approach [13,14]. The
obtained nano-objects can exhibit different morphologies dictated
by the relative volume fractions of each block (e.g. by altering their
molar masses). In all cases, the hydrophilic segment covalently
anchored at the particle surface will ensure the stabilization.
The transposition of these concepts, namely the synthesis of
amphiphilic block copolymers in water, for the formation of film-
forming latexes is thus appealing [15]. In this perspective, we
have formerly reported the successful use of a poly(ethylene oxide)
macroRAFT agent carrying a dodecyl hydrophobic group attached
to the trithiocarbonate function (PEO-TTC) in the RAFT emulsion
copolymerization of VDC and methyl acrylate [16]. Stable PVDC-
based latexes with a 10% solids content were formed using 6.0 wt
% of PEO-TTC (based on monomers). The synthesis of PVDC-based
latexes using a preformed poly(acrylic acid)-b-polystyrene
amphiphilic block copolymer (10 wt% for a solids content
comprised between 10 and 30 wt%) carrying a trithiocarbonate
group was also reported shortly after [17]. Industrially relevant
recipes should however achieve higher solids content while using
lower amounts of macroRAFT agent, which would act as an (elec-
tro)steric stabilizer (in situ formation of stabilizing amphiphilic
block copolymers) with no control over the growth of the polymer
chains composing the particle core. In that sense, it could be
assimilated to a reversible and efficient transurf macromolecule
[18e20].
The present paper describes the successful implementation of
this strategy using water-soluble polymers obtained by RAFT for
the production of surfactant-free PVDC latexes in a one-pot/two-
step process that is exclusively conducted in water. The aim of
this study is to provide industrially viable PVDC latexes, without
molecular surfactants but with the same (or better) properties than
the ones commercially available for coating applications.
2. Experimental section
2.1. Materials
Methyl acrylate (MA, Aldrich, 99%) was vacuum distilled before
use. Vinylidene chloride (VDC, Acros Organics, 99.9%) was washed
with a 25 wt% NaOH aqueous solution and dried on MgSO4 before
use. Acrylic acid (AA, Aldrich, 99%), methacrylic acid (MAA, Acros
Organics, 99.5%), sodium 4-styrenesulfonate (SSNa, Aldrich,
>99.5%), 4,4-azobis(4-cyanopentanoic acid) (ACPA, Aldrich, >98%),
ammonium persulfate (APS, Acros Organics. 98%), tetrasodium
pyrophosphate (TSPP, Sigma, >95%), 1,4-dioxane (Sigma-Aldrich,
>99.5%) were used as received. 4-Cyano-4-thiothiopropylsulfanyl
pentanoic acid (CTPPA) was synthesized following the procedure
described in a previous paper [21].
2.2. Characterization techniques
2.2.1. Nuclear magnetic resonance (NMR)
The conversion of AA, MAA and SSNa was determined by 1H
NMR spectroscopy (300 MHz Bruker) in D2O at room temperature
by the relative integration of the protons of the internal reference
(1,3,5-trioxane) at 5.1 ppm and the vinylic protons of AA (at 5.9, 6.1
and 6.3 ppm), MAA (at 5.6 and 6.0 ppm) or SSNa (at 5.4 and
5.9 ppm).
2.2.2. Size exclusion chromatography (SEC-THF)
The polymers were analyzed at a concentration of 3 mg mL
1
after filtration through a 0.45 mm pore-size membrane. Measure-
ments were performed in THF at 40  C at a flow rate of 1 mL min
1
with toluene as flow rate marker. The separation was carried out on
three columns from Malvern Instruments [T6000 M General Mixed
Org (300  8 mm)]. The setup (Viscotek TDA305) was equipped
with a differential refractive index (RI) detector (l ¼ 670 nm) and a
diode array UV detector. Before analysis, the polymers containing
AA or MAA units were modified by methylation of the carboxylic
acid groups using trimethylsilyl diazomethane. The number-
average molar mass (Mn), the weight-average molar mass (Mw)
and the dispersity (Ð ¼ Mw/Mn) were calculated from the RI de-
tector with a calibration curve based either on poly(methyl meth-
acrylate) standards (PMMA, from Polymer laboratories) for the
analysis of the methylated PMAA macroRAFT agents, or on poly-
styrene standards (PS, from Polymer Laboratories) for the analysis
of the methylated PAA macroRAFT agents and the polymer latexes.
2.2.3. Aqueous size exclusion chromatography (ASEC)
The PSSNa macroRAFT agents were analyzed at a concentration
of 4 mg mL
1 after filtration through a 0.45 mm pore-size mem-
brane. Measurements were performed in aqueous solution of
NaNO3 (0.3 mol L
1) and NaH2PO4 (0.01 mol L
1) (pH ¼ 9) at 22  C
and at a flow rate of 0.5 mL min
1. The separation was carried out
on two columns PL aquagel OH-30. The setup was composed of a
pump Isochrom LC plus a sampler 717 Plus (Waters) and was
equipped with multi-angle laser light scattering (MALLS) detector
Wyatt EOS in line with a differential refractive index (RI) detector
Wyatt Optilab T-rex (l ¼ 658 nm). Mn and Ð were calculated from
the MALLS detector by using a dn/dC ¼ 0.195 mL g
1 [22].
2.2.4. Matrix assisted laser desorption ionization-time of flight
mass spectrometry (MALDI-ToF MS)
MALDI-ToF spectra of PSSNa were acquired on a Voyager-DE STR
(AB Sciex). This instrument was equipped with a nitrogen laser
(wavelength 337 nm) to desorb and ionize the samples. First so-
dium ions were removed from the samples thanks to a cationic
exchange resin until aqueous solutions of polysulfonic acid of pH
lower than 2 were obtained. Samples were analyzed using trans 3-
indoleacrylic acid as a matrix. The accelerating voltage used was
20 kV. The spectra were the sum of 300 shots, and an external mass
calibration was used. Samples were prepared by dissolving the
product in THF at a concentration of 1 g L
1.
 E. Velasquez et al. / Polymer 106 (2016) 275e284
2.2.5. Dynamic light scattering (DLS)
The z-average particle diameter (Dz) and the dispersity factor of
highly diluted samples (Poly) were measured by dynamic light
scattering (DLS) (NanoZS from Malvern Instruments) at 173 at
25  C.
2.2.6. Transmission electron microscopy (TEM)
The diluted samples were dropped on a carbon-coated copper
grid and dried under air. The TEM images were recorded without
staining using a Philips CM120 microscope operating at an accel-
erating voltage of 80 kV (Centre Technologique des Microstruc-
tures, platform of the Universite
Claude Bernard Lyon 1,
Villeurbanne, France). The number- and mass-average particle di-
ameters (Dn and Dw, respectively) as well as the particle-diameter
dispersity (Dw/Dn) were determined using AnalySIS software (Soft
Imaging System). Some samples were observed in their natural
hydrated environment using cryogenic TEM (cryo-TEM). The
diluted samples were dropped onto 300 Mesh holey carbon films
(Quantifoil R2/1) and immediately quench-frozen in liquid ethane
using a Leica EM CPC workstation (Leica Microsystems, Austria).
The grid was then mounted on a precooled Gatan 626 specimen
holder, transferred in the Philips CM120 microscope operating at an
accelerating voltage of 120 kV.
2.2.7. UV/vis spectrophotometry
The hydrolytic stability of the trithiocarbonate extremity of the
PAA, PMAA and PSSNa macroRAFT agents was studied by UV/vis
spectrophotometry (JASCO V-530) using quartz cells. Septum-
sealed round-bottom flasks of aqueous solutions of PAA-CTPPA
(PAA3, Mn ¼ 2200 g mol
1 (Table S1), C ¼ 1.7 mmol L
1;
[TSPP] ¼ 35 mmol L
1; pH ¼ 6.6), PMAA-CTPPA (PMAA2,
Mn ¼ 2400 g mol
1 (Table S2), C ¼ 0.9 mmol L
1;
[TSPP] ¼ 35 mmol L
1; pH ¼ 8.1) and PSSNa-CTPPA (PSSNa5,
Mn ¼ 4800 g mol
1 (Table S3), C ¼ 3.3 mmol L
1; pH ¼ 4) were
immersed in an oil bath thermostated at 70  C and stirred for 5 h.
Samples were periodically withdrawn to follow the evolution of the
UV signal of the trithiocarbonate function at 309 nm.
2.2.8. Tensiometry
Surface tension (ST) measurements were carried out on a Krüss
tensiometer thermostated at 25  C. The aqueous macroRAFT solu-
tion or the latex was stirred for 15 min to reach the equilibrium
temperature and the surface tension was measured using the
Wilhelmy plate method.
2.2.9. pH measurements
The pH values of the aqueous solutions were measured with a
Mettler Toledo SevenEasy pH-meter using a InLab Routine Pro
electrode. For the latexes, a InLab Science Pro electrode was used. In
all cases, the electrodes were calibrated with 4.01, 7.00, and 10.00
pH buffer solutions from Mettler Toledo.
2.3. One-pot procedure for the synthesis of surfactant-free PVDC
latexes from PAA, PMAA or PSSNa hydrophilic macroRAFT agents
Step 1: Synthesis of the hydrophilic PAA-, PMAA- and PSSNa-
CTPPA macroRAFT agents in water.
The synthesis of all the macroRAFT agents followed the same
procedure. Polymerizations of AA, MAA or SSNa in water were
carried out in a septum-sealed flask, using ACPA as an initiator and
CTPPA as a RAFT agent. The mixture was purged for 30 min with
nitrogen and then immersed in a thermostated oil bath heated to
80  C (for MAA or SSNa) or 70  C (for AA or SSNa), which corre-
sponded to time zero of the polymerization The overall monomer
277
conversion was determined by 1H NMR spectroscopy of the crude
reaction medium diluted with D2O.
In a typical experiment (PMAA2, Mn,th ¼ 2039 g mol
1, Table S2),
319.0 mg of CTPPA (1.15 mmol), 32.9 mg of ACPA (1.17  10
1 mmol)
and 372.9 mg of 1,3,5-trioxane (4.14 mmol) were dissolved in 2.04 g
of MAA (23.7 mmol). 22.52 g of water were then added. It is worth
mentioning that the resulting mixture was initially not perfectly
homogeneous but quickly cleared up once the polymerization
started. The same observation was made for AA and SSNa poly-
merizations. The regular withdrawal of samples allowed following
the monomer conversion as a function of time and the evolution of
molar masses and molar mass distributions as a function of
monomer conversion. The detailed experimental conditions and
macromolecular features of all the synthesized macroRAFT agents
are gathered in Tables S1eS3 (Supporting Information).
Step 2: Emulsion copolymerization of VDC and MA mediated by
hydrophilic macroRAFT agents.
Emulsion polymerizations were performed in a Parr glass
reactor equipped with a four-blade stirrer, an internal temperature
probe and a nitrogen inlet. In a typical experiment (PMAA-L1,
Table 1) a given quantity of macroRAFT solution (1.6900 g,
36.8 mmol L
1) synthesized in Step 1 (i.e. PMAA3,
Mn,exp ¼ 2500 g mol
1, Ð ¼ 1.29) was diluted with water (73.5 g) to
obtain the required concentration of PMAA-CTPPA
(82.9 mmol L
1
1
water). Then APS (68.1 mg, 3.98 mmol L water) and
TSPP (702 mg, 35.2 mmol L
1water) were added to the reaction
mixture. The latter was then introduced in the reactor and purged
with nitrogen at room temperature. After deoxygenation by
bubbling with nitrogen for 20 min, MA (5.2 mL, 57.7 mmol) and
VDC (38 mL, 475 mmol) were added via the injection valve in the
reactor. Then the autoclave was pressurized with 1 bar of nitrogen
and the reaction mixture heated to 70  C and stirred at 400 rpm.
Samples were withdrawn to measure the overall weight monomer
conversion by gravimetric analysis, along with particle size analysis
by DLS. After 2.8 h of reaction, the reactor was depressurized, and
the latex stripped from the residual monomers under nitrogen
bubbling and gentle stirring during 1 h. Experiments performed
with PAA-CTPPA, PMAA-CTPPA and PSSNa-CTPPA are collated in
Tables 1e3, respectively.
3. Results and discussion
3.1. Synthesis of the macroRAFT agents
3.1.1. PAA and PMAA macroRAFT agents
The synthesis of PAA-CTPPA and PMAA-CTPPA has been
described in details in our previous studies [23e25]. Briefly, a series
of both types of macroRAFT agents was synthesized in water using
CTPPA as a RAFT agent and ACPA as an initiator, targeting molar
masses close to 2000 g mol
1 (for PAA and PMAA) or 4000 g mol
1
(for PMAA). Two typical kinetic studies are presented in the Sup-
porting Information (Figs. S1 and S2), as well as the detailed
characteristics of all the batches that will be subsequently used in
the emulsion copolymerization of VDC and MA (Tables S1 and S2).
Whatever the targeted molar mass, well-defined PMAA or PAA
macroRAFT agents with controlled features were obtained with
narrow molar mass distributions.
3.1.2. PSSNa macroRAFT agents
RAFT polymerization of sodium 4-styrenesulfonate in pure
water has been only scarcely studied [26e32]. The first example of
PSSNa macroRAFT agent synthesis was performed in water at 70  C
with ACPA as initiator in the presence of a dithiobenzoate-type
278 E. Velasquez et al. / Polymer 106 (2016) 275e284

Table 1
Experimental conditions of the emulsion copolymerization of VDC and MA in the presence of the PAA-CTPPA macroRAFT agent and characterization of the latex obtained.a

Exp. macroRAFT VDC (mol%)c tth (%)d Time (h) Conv. (wt%)e texp (%)f Coag (wt%)g Mn,exp (kg mol
1) (Ð)h Dz (nm) (Poly)i pHfinal
Batch Mn,exp (g mol
1) (wt%)b

PAA-L1 PAA2 2000 0.50 70 40 5.3 100 40.0 0 75.6 (2.7) 443 (0.18) 6.1
PAA-L2 PAA2 2000 0.50 80 40 6.5 100 38.9 2.8 58.5 (3.0) 414 (0.27) 6.0
PAA-L3 PAA3 2200 0.50 89 40 7.0 79 25.5 8.5 31.6 (2.9) 457 (0.22) 6.4
a
T ¼ 70  C; [TSPP] ¼ 35 mmol L
1water; [APS] ¼ 3.9 mmol L
1water.
b
Percentage by weight of PAA-CTPPA with respect to the monomers ¼ m0-PAA-CTPPA/(m0-PAA-CTPPA þ m0-M)  100.
c
Percentage by mole of VDC in the monomer mixture: mol%VDC ¼ n0-VDC/n0-M  100, with n0-M ¼ n0-VDC þ n0-MA.
d
Targeted solids content (wt%): tth ¼ m0-M/m0-total, with m0-M ¼ m0-VDC þ m0-MA.
e
Monomer overall weight conversion determined by gravimetry.
f
Final solids content taking into account the amount of polymer for the given conversion, after filtration of the coagulum (if present).
g
Weight fraction of coagulum ¼ mcoagulum/(m0-M þ m0-macroRAFT)  100.
h
Determined by SEC-THF with a PS calibration curve. Mn,exp are those of the methylated polymers.
i
Obtained by DLS.

Table 2
Experimental conditions of the emulsion copolymerization of VDC and MA in the presence of the PMAA-CTPPA macroRAFT agent and characterization of the latex obtained.a

Exp. macroRAFT [TSPP] tth (%)c Time (h) Conv. (wt%)d texp (%)e Coag (wt%)f Mn,exp (kg mol
1) Dz (nm) pHfinal
(mmol L
1water) (Ð)g (Poly)h
Batch Mn,exp (wt%)b
(g mol
1)

PMAA-L1 PMAA3 2500 0.30 35 40 2.8 100 39.2 2.8 61.7 (2.9) 144 (0.03) 6.2
PMAA-L2 PMAA4 2300 0.30 24 40 3.1 95 37.0 1.9 57.1 (2.7) 148 (0.05) 6.2
PMAA-L3 PMAA4 2300 0.31 10 40 2.8 85 30.2 9.5 59.9 (2.4) 211 (0.21) 4.6
PMAA-L4 PMAA5 2300 0.30 0 40 5.0 100 35.4 11.8 50.5 (2.4) 255 (0.02) 1.9
PMAA-L5 PMAA6 3800 0.62 35 39 2.9 100 37.8 2.5 62.6 (2.8) 136 (0.08) 6.2
a
T ¼ 70  C; VDC: 89 mol%; [APS] ¼ 3.9 mmol L
1water.
b
Percentage by weight of PMAA-CTPPA with respect to the monomers ¼ m0-PMAA-CTPPA/(m0-PMAA-CTPPA þ m0-M)  100.
c
Targeted solids content (wt%): tth ¼ m0-M/m0-total, with m0-M ¼ m0-VDC þ m0-MA.
d
Monomer overall weight conversion determined by gravimetry.
e
Final solids content taking into account the amount of polymer for the given conversion, after filtration of the coagulum (if present).
f
Weight fraction of coagulum ¼ mcoagulum/(m0-M þ m0-macroRAFT)  100.
g
Determined by SEC-THF with a PMMA calibration curve. Mn,exp are those of the methylated polymers.
h
Obtained by DLS.

Table 3
Experimental conditions of the emulsion copolymerization of VDC and MA in the presence of the PSSNa-CTPPA macroRAFT agent and characterization of the latex obtained.a

Exp. macroRAFT Time (h) Conv. (wt%)e texp (%)f Coag. (wt%)g Dz (nm) (Poly)h ST (mN m
1)i

Batch Mn,exp (g mol
1) (wt%)d

b
PSSNa-L1 PSSNa4 2162 0.50 3.1 100 37.4 6.2 93 (0.05) 72.3
PSSNa-L2 PSSNa4 2162b 1.00 3.1 100 39.3 1.8 79 (0.06) 64.0
PSSNa-L3 PSSNa1 3900c 1.95 3.2 100 39.7 1.3 70 (0.13) 68.2
PSSNa-L4 PSSNa5 4800c 1.96 3.3 100 40.2 0.9 66 (0.08) 71.8
PSSNa-L5 PSSNa6 7500c 1.92 3.3 100 39.5 1.7 77 (0.06) ND
a
T ¼ 70  C; VDC: 89 mol%; Targeted solids content: tth ¼ 40 wt%; [APS] ¼ 3.9 mmol L
1water; no TSPP.
b
Experimental number-average molar mass of PSSNa-CTPPA determined by MALDI-ToF mass spectrometry.
c
Experimental number-average molar mass of PSSNa-CTPP determined by ASEC.
d
Percentage by weight of PSSNa-CTPPA with respect to the monomers ¼ m0-PSSNa-CTPPA/(m0-PSSNa-CTPPA þ m0-M)  100.
e
Monomer overall weight conversion determined by gravimetry.
f
Final solids content taking into account the amount of polymer for the given conversion, after filtration of the coagulum (if present).
g
Weight fraction of coagulum ¼ mcoagulum/(m0-M þ m0-macroRAFT)  100.
h
Obtained by DLS.
i
Latex surface tension (ST) measured via the Wilhelmy plate method at 25  C.

RAFT agent, 4-cyano-4-((phenylcarbonothioyl)thio) pentanoic acid.
The molar mass of the obtained polymer was 8000 g mol
1 with a
dispersity of 1.13 [26]. Using similar experimental conditions,
Mitsumaki et al. also produced PSSNa polymers with controlled
molar masses in good agreement with the theoretical ones. The
resulting polymers were then used to form double hydrophilic
block copolymers [27]. The same combination of initiator and RAFT
agent was utilized by Yeole et al. to synthesize PSSNa macroRAFT
agents later used in emulsion polymerization [30e32]. Mertoglu
et al. polymerized SSNa in water at 55  C using a fluorescent labeled
RAFT agent [29]. Stimuli responsive diblock and triblock co-
polymers were also obtained from this macroRAFT [28]. Finally,
Barsbay et al. [33] carried out SSNa polymerization at ambient
temperature under g-irradiation in a mixture of water/ethanol: 93/
7 (v/v), EtOH allowing a complete solubilization of the RAFT agents.
Two RAFT agents were tested: the above mentioned 4-cyano-4-
((phenylcarbonothioyl)thio) pentanoic acid and 3-
benzylsulfanylthiocarbonylsulfanyl propionic acid, a
trithiocarbonate-type RAFT agent. The experiments in the presence
of the dithiobenzoate RAFT agent displayed the features of a
controlled polymerization whereas it was not the case with the
trithiocarbonate RAFT agent with a non-linear evolution of the
molar masses with conversion and relatively high dispersities
(between 1.5 and 1.9). In consequence, to the best of our
 E. Velasquez et al. / Polymer 106 (2016) 275e284 279

knowledge, there is no example of successful controlled polymer-
ization of SSNa in presence of a trithiocarbonate RAFT agent in
water. CTPPA was thus evaluated as controlling agent in the poly-
merization of SSNa in water initiated by ACPA. The influence of both
the temperature and CTPPA concentration was investigated. The
SSNa conversion was determined by 1H NMR in D2O and the
resulting polymers were characterized by ASEC (Table S3 in the
Supporting Information).
As expected, the polymerization was faster at 80  C (PSSNa1)
than at 70  C, for which complete conversion was reached in 5 h
(PSSNa2, Fig. 1a), whereas only 3 h were necessary at 80  C. In both
cases however, well-defined PSSNa chains with a very narrow
distribution (Ð ¼ 1.02) were formed. The initial amount of CTPPA
was then varied (at 70  C) to target two different degrees of poly-
merization (i.e. DPn,th ¼ 20 or 44). The kinetic profile was similar for
the two reactions (Fig. 1b). The ASEC traces of the polymers were
narrow and shifted toward higher molar masses with increasing
monomer conversion (DPn,th ¼ 44, Fig. 1c). The absolute number-
average molar mass values (obtained from the light scattering de-
tector) increased linearly with monomer conversion and were close
to the theoretical ones, while dispersities remained very low
throughout the polymerization (Fig. 1d). All these results demon-
strate that CTPPA is an effective RAFT agent for the synthesis of
well-defined PSSNa in aqueous medium.
The living features of the PSSNa chains were further demon-
strated by MALDI-ToF analyses on a low molar mass sample
(PSSNa4, see Figs. S3 and S4 and Table S4 in the Supporting
Information).
3.2. Synthesis of surfactant-free PVDC latexes mediated by
hydrophilic macroRAFT agents
The various macroRAFT agents synthesized in the previous
section were then evaluated as reactive stabilizer for the stabili-
zation of PVDC latexes. In all cases, a one-pot/two-step protocol
entirely conducted in water was followed: 1) synthesis of the
macroRAFT agent in water (as just depicted); 2) direct use of the
aqueous solution of the macroRAFT agent in the emulsion poly-
merization step.
As mentioned in the Introduction, VDC is usually copolymerized
with a comonomer allowing the formation of a semi-crystalline
polymer easy to handle. Nevertheless, in order to maintain inter-
esting barrier properties, the amount of this comonomer should
not exceed 20 mol%. In the present study, the selected comonomer
was methyl acrylate (MA), commonly used in copolymerization
with VDC. The reactivity ratios for this pair of monomers are both
close to 1 [6,34,35], which means that random copolymers with a
composition close to that of the initial monomer mixture should
form. This composition could however be slightly affected by the
different solubility of the two monomers in water (higher for MA
[36] than for VDC [6]), with the formation in water of a very low
fraction of polymer chains enriched in MA.
In all emulsion copolymerization experiments, ammonium
persulfate (APS) was used as the initiator despite the fact that side
oxidation reaction of dithiobenzoate RAFT agents has been reported
in the presence of potassium persulfate (KPS) [37]. Indeed, no
degradation of the trithiocarbonate function was observed by Luo
et al. when initiating styrene emulsion polymerization by KPS, in
the presence of 2-(((dodecylsulfanyl) carbonothioyl)sulfanyl)
propanoic acid (as molecular RAFT agent) and of PAA-b-PS macro-
RAFT agents originating from the same RAFT agent (as stabilizer)
[38]. Besides, persulfate initiators display higher decomposition
rate than ACPA (for instance kd, KPS ¼ 5.01  10
2 s
1 [39] and kd,

5
1
s [40] in water at 70  C and 69  C, respectively).
ACPA ¼ 1.9  10
APS is also widely used in industry because of a higher solubility in
water than KPS.

a) b)
Conv. Conv.
100 (%) 100 (%)

80 80

60 60

40 40 T = 70 °C
DP n,th = 20

20 80 °C (PSSNa1) 20 DP n,th = 20 (PSSNa2)

70 °C (PSSNa2) DP n,th = 44 (PSSNa3)
0 0
0 60 120 180 240 300 360 0 60 120 180 240 300 360
Time (min) Time (min)
c) 78 % 59 % Normalized LS
d) Mn (g mol-1) Ð
44 %
10000 1.8
98 %

8000
1.6

6000
1.4
4000
conv.
1.2
2000

0 1.0
0 20 40 60 80 100
Ve (mL) Conv. (%)

Fig. 1. RAFT polymerization of SSNa performed in water with [SSNa]0 ¼ 0.69 mol L
1 and [CTPPA]0/[ACPA]0 ¼ 10. Evolution of the monomer conversion versus time (a) at 80  C and
70  C (DPn,th ¼ 20), and (b) for DPn,th ¼ 20 or 44 (T ¼ 70  C). (c) ASEC chromatogram evolution with conversion (Light scattering (LS) signal) for DPn,th ¼ 44 at 70  C (PSSNa3). (d)
Corresponding evolution of the number-average molar mass Mn (LS) (full symbols) and Ð ¼ Mw/Mn (open symbols) versus conversion. The straight line corresponds to the
theoretical evolution of Mn with conversion.
280 E. Velasquez et al. / Polymer 106 (2016) 275e284
3.2.1. PAA-CTPPA mediated emulsion polymerization
A series of emulsion copolymerizations of VDC and MA was first
carried out with various amounts of MA (from 11 to 30 mol%), using
0.5 wt% of macroRAFT agent (Mn,exp z 2000 g mol
1) and targeting
a solids content close to 40 wt% (PAA-L1 to PAA-L3, Table 1). To
prevent a too strong acidification of the medium (due to dehy-
drochlorination of the polymer during the reaction process [35]),
TSPP was used as pH regulator to scavenge HCl, and the final pH
was close to 6. PAA chains were thus likely partially ionized [41].
Our previous study with similar PAA macroRAFT agents showed the
strong influence of the pH on the outcome of the polymerization
[23,42]. We thus checked the stability of the trithiocarbonate chain
end in the presence of TSPP using concentrations similar to those
used for the emulsion polymerization. As shown in Fig. 2, and as
observed in our previous study, the thiocarbonylthio function
remained stable over 5 h, with less than 1% loss.
Regardless of the VDC/MA ratio, the final particle size and size
distribution were similar for the three latexes (Dz ca. 440 nm, Poly
0.22). Their colloidal stability was however significantly different.
Whereas no coagulum was collected at the end of the reaction
performed with the highest fraction of MA (i.e. 30 mol%), the two
other latexes showed an increasing amount of coagulum as MA
content was lowered (2.8 and 8.5 wt%, for 20 and 11 mol% of MA,
respectively). We showed in our previous work that increasing the
amount of MA in the solution copolymerization of VDC and MA
mediated by a PAA macroRAFT agent could enhance the transfer
reaction. Indeed, the higher the initial fraction of MA, the higher the
chain transfer constant [43]. This chain transfer reaction occurring
at the very beginning of the polymerization is of paramount
importance since it will ensure the quality of the nucleation by a
rapid formation of the amphiphilic stabilizer. Consequently, the
better stability obtained for the PAA-L1 latex probably lies in a
better efficiency of anchoring of the PAA segment onto the particles.
This seems to be confirmed by the chromatograms of the final la-
texes, which shows the presence of residual PAA macroRAFT agent
when 11 mol% of MA were used (Fig. 3). Eventually, the molar mass
of the final polymer decreased when the amount of VDC increased,
which could be correlated with the high transfer constant value to
VDC monomer (Ctr ¼ 6.4  10
3) [44].
Relative loss of
absorbance @ 309 nm
50%
40%
30%
PAA-CTPPA
20% PMAA-CTPPA
PSSNa-CTPPA
10%
0%
0 60 120 180 240 300
Time (min)
Fig. 2. Evolution of the relative loss of absorbance of the thiocarbonylthio function
versus time for the three kind of macroRAFT agents used in this study: PAA-CTPPA
(PAA3), PMAAeCTPPA (PMAA2) and PSSNa-CTPPA (PSSNa5) (see the experimental
part for detailed conditions of analyses).
However, the composition of PVDC-based latexes should not
include more than 10e20 mol% of MA to keep the barrier proper-
ties. Indeed, below 10% the obtained copolymer is too crystalline to
film-form [6]. Despite the fact that a stable and high solids content
latex (with however large particles) could be obtained using 30 mol
% of MA, alternative strategies were developed for the formation of
stable PVDC latexes incorporating no more than 11 mol% of MA. The
first one was to use the methacrylate homologue of PAA, PMAA,
which should a priori provide a better leaving group for the RAFT
polymerization of a 1,1-disubstituted monomer such as VDC.
3.2.2. PMAA-CTPPA mediated emulsion polymerization
The first experiment (PMAA-L1) was performed with a PMAA
macroRAFT agent of 2500 g mol
1 following a recipe similar to that
of PAA-L3, i.e. using the same VDC, MA (11 mol%), APS and TSPP
(leading to a final pH of 6.2) concentrations and targeting a solids
content of 40 wt% (Table 2). The percentage of PMAA macroRAFT
agent was diminished to 0.3 wt%. The conversion reached 100% in
less than 3 h. A certain amount of coagulum (2.8 wt%) was again
observed, but less than with PAA (8.5 wt%) although less macro-
RAFT agent was used (0.3 wt% for PMAA-L1 versus 0.5 wt% for PAA-
L3). The obtained latex indeed showed better colloidal features
than its PAA-counterpart. The particle size was decreased (from
Dz ¼ 457 nm to 144 nm) with a much narrower particle size dis-
tribution (Poly ¼ 0.03 versus 0.22) (see TEM image in Fig. 4a). This
positive result supports the assumption that the PMAA macroRAFT
agent effectively allowed a more efficient chain extension of the
PMAA hydrophilic chains with VDC and MA units, even for low MA
content, leading to the very fast formation of amphiphilic block
copolymers able to provide a good stabilization of the latex. This is
further supported by the absence of any residual macroRAFT agent
in the final sample (Fig. 4b).
However, our previous study on styrene emulsion polymeriza-
tion mediated by PMAA macroRAFT agents in PISA conditions (i.e.
using 5 wt% of PMAA) [24] showed that some of the PMAA chains
might have lost their RAFT extremity at pH 6.5 or higher. The hy-
drolytic stability of the RAFT function was thus evaluated under the
conditions employed in this study and following the intensity of the
UV signal of the trithiocarbonate chain end at 309 nm. A solution of
PMAA and TSPP was prepared (using the same concentrations as in
latex PMAA-L1) and heated at 70  C for 5 h (Fig. 2). The loss in
functionality after 1 h at pH 8 was 23%. During the copolymeriza-
tion of VDC and MA, the initial pH was close to 8 and dropped to 6
in 1 h owing to both the presence of VDC and the APS decompo-
sition, which likely minimizes the extent of chain end hydrolysis. In
addition, at that stage, the nucleation has already begun (as attes-
ted by the milky aspect of the medium) and the trithiocarbonate
function is buried in the core of the particles.
To see whether the amount of TSPP (i.e. the pH) had an impact
on the polymerization, three additional experiments were per-
formed using lower TSPP concentrations, or even no TSPP at all
(Latex PMAA-L2 to PMAA-L4, Table 2). In the first run (Latex PMAA-
L2, [TSPP] ¼ 24 mmol L
1), the outcome of the polymerizations was
quite similar to the previous one, in terms of particle size, particle
size distribution, final pH, the only slight differences being
observed in the final conversion and the amount of coagulum.
Conversely, the second experiment (Latex PMAA-L3,
[TSPP] ¼ 10 mmol L
1) showed significant differences. The con-
version was lowered to 85%, associated with a high amount of co-
360
agulum (9.5 wt%). Accordingly, the particle size was higher
(Dz ¼ 211 nm) and more heterogeneous (Poly ¼ 0.21). All the data
indicate a lower stability of the particles, likely related to the pH
value, which reached 4.6 at the end of the reaction. This negative
trend was even more striking when no TSPP was used (Latex PMAA-
L4, pH ¼ 1.9; 5 h, bigger particle size and more coagulum). When
 E. Velasquez et al. / Polymer 106 (2016) 275e284 281

Fig. 3. Comparison of the size exclusion chromatograms of the starting PAA macroRAFT agent with those of the final latexes obtained from the emulsion copolymerizations of VDC
and MA performed with various amounts of MA and: a) 30 mol% (PAA-L1), b) 20 mol% (PAA-L2) and c) 11 mol% (PAA-L3), in the presence of 0.50 wt% (with respect to the monomers)
of PAA-CTPPA (See Table 1 for detailed experimental conditions).

Fig. 4. a) TEM image of the latex PMAA-L1 obtained from the emulsion copolymerization of VDC and MA in the presence of 0.30 wt% (with respect to the monomers) of PMAA-
CTPPA (PMAA3). b) Size exclusion chromatograms of PMAA3 and PMAA-L1.

the pH value is lower than the pKa value (5.9) of this macroRAFT
agent [45], most of the PMAA chains are not ionized and thus less
hydrophilic. They adopt a coil conformation that is less favorable for
stability than a (partially) deprotonated homologue [24].
A last experiment investigating the impact of the molar mass of
the PMAA macroRAFT was performed using, in the presence of
TSPP, a higher molar mass macroRAFT agent
(Mn,exp ¼ 3800 g mol
1, PMAA6) introduced at the same molar
concentration (meaning that its weight fraction was higher than for
PMAA-L1, i.e. 0.6 wt% - PMAA-L5, Table 2). The particle diameter
and the amount of coagulum were both slightly lower than the ones
obtained in PMAA-L1. The colloidal features of the latex (which in
the end also includes more hydrophilic species) were thus not
significantly improved.
To confirm that all PMAA chains have effectively been grafted
onto the particle surface, surface tension measurements were car-
ried out (Fig. 5). The surface tension measured for the latex PMAA-
L5 (71.9 mN m
1) was really close to that of the deionized water
used in our laboratory (72.3 mN m
1). If present, the concentration
of unreacted macroRAFT agent would thus be lower than
2.9  10
7 mol L
1 for which a surface tension of 70.4 mN m
1 was
measured. Hydrosoluble species arising from initiator decomposi-
tion could also be formed and contribute to the surface tension. The
surface tension data are thus consistent with the presence of very
low amounts of hydrophilic species and with an almost
quantitative consumption of the PMAA macroRAFT agent.
Though successful stabilization was achieved with a very low
content of PMAA macroRAFT agent, this process remains pH
dependent and some coagulum is usually collected at the end of the
reaction. While the latter can be overcome by process engineering
(which is not the topic of this paper), a last macroRAFT agent was
investigated to provide a pH-independent process. To this aim,
permanently charged PSSNa macroRAFT agents were synthesized
(vide supra) and used in emulsion copolymerization of VDC and MA.
This kind of macroRAFT agent would avoid the use of TSPP, which
dramatically increases the ionic strength of the medium and likely
leads to a (partial) screening of the charges of the PMAA macro-
RAFT, thus negatively impacting the stability of the latex.
3.2.3. PSSNa-CTPPA mediated emulsion polymerization
The use of PSSNa macroRAFT agent for the stabilization of
surfactant-free latexes has only been reported by one team mostly
for the polymerization of styrene [30,31], using three dithio-
benzoate PSSNa macroRAFT agents of 1200, 46,800 and
116,000 g mol
1. The particle size could be tuned by both the molar
mass and the amount of macroRAFT agent (either 2 or 10 wt%). The
same authors also studied MMA, BA and their copolymerization
with styrene [32]. However, the conversion systematically pla-
teaued at 80% and the solids content of the final latexes was limited
to 10 wt%.
282 E. Velasquez et al. / Polymer 106 (2016) 275e284

72.5 72.3 indicate that the stabilization capability of PSSNa was higher than
that of PMAA. However, it should also be noted that although the
70 two compared macroRAFT agents have similar molar masses (ca.
2200 g mol
1 for PSSNa and 2500 g mol
1 for PMAA), the molar
67.5
concentration was however almost doubled in the case of the
65 PSSNa macroRAFT agent. A direct comparison between the two
experiments is not possible here (different amount of macroRAFT
62.5 agent and different pH, which impacts the rate of radical pro-
60 duction, higher at acidic pH).
ST (mN m-1)

In the next experiment the amount of PSSNa macroRAFT agent

57.5
55
52.5
50
47.5
macroRAFT
45
PMAA-L5
42.5
water
40
1.E-07 1.E-05 1.E-03 1.E-01
[PMAA-CTPPA]0 (mol L-1)
Fig. 5. Surface tension measurement for latex PMAA-L5, compared to that of water and
various aqueous solutions of PMAA-CTPPA.
Our PSSNa macroRAFT agents were used in emulsion copoly-
merization of VDC and MA at 40 wt% solids content to match the
best results obtained in the presence of PMAA-CTPPA. A pre-
liminary polymerization experiment performed with TSPP led to
the destabilization of the latex, likely induced by the high ionic
strength as mentioned above (data not shown). Thus the next
experiment was performed with 0.5 wt% of a PSSNa macroRAFT
agent of 2160 g mol
1 (latex PSSNa-L1, Table 3), in the absence of
TSPP. The hydrolytic stability study of PSSNa-CTPPA showed that
the thiocarbonylthio function remained stable over 5 h, with less
than 3% loss (Fig. 2). In the emulsion experiment, the initial pH
was close to 4 and decreased to 2 by the end of the polymeriza-
tion. Complete conversion was reached in about 3 h. The amount
of coagulum was however quite high (6.2 wt%) for this experi-
ment. The particles obtained with PSSNa were smaller than those
formed with PMAA (93 nm versus ca. 140 nm). This seems to
was doubled (1 wt%, PSSNa-L2), impacting both the particle size
and their stability: the diameter decreased to 79 nm while
considerably less coagulum was formed (1.8 wt%). Using the same
molar amount of a higher molar mass PSSNa
(Mn,exp ¼ 3900 g mol
1, Latex PSSNa-L3), with consequently a
higher weight fraction (ca. 2 wt%), led to the decrease of both the
particle diameter (70 nm) and the amount of coagulum (1.3 wt%).
This trend was confirmed when the molar mass of the macroRAFT
agent was further increased (Mn,exp ¼ 4800 g mol
1, Latex PSSNa-
L4): Dz ¼ 66 nm, with 0.9 wt% of coagulum (see the correspond-
ing TEM images in Fig. 6). This effect was less pronounced with the
PMAA macroRAFT agents. On the other hand, increasing further the
molar mass of the macroRAFT agent while maintaining the same
1.E+01
weight fraction (Mn,exp ¼ 7500 g mol
1, PSSNa-L5) did not bring any
improvement to the system.
Unfortunately, the lack of a common solvent for P(VDC-co-MA)
and PSSNa blocks prevented SEC analysis. Nevertheless, surface
tensions measurements showed high values, sometimes close to
that of water (from 64 mN m
1 to 72.3 mN m
1, Table 3), sup-
porting an almost quantitative covalent anchoring of the PSSNa
chains to the particles, together with a small amount of hydrophilic
species, as described in the case of PMAA.
The minimum film-forming temperature and the glass transi-
tion temperature of some selected latexes were finally measured
(Table 4), showing that these latexes were able to form films at
ambient temperature. Moreover, when a film obtained from latex
PSSNa-L4 was dipped in water for a couple of hours at 95  C, no
whitening was observed (no opacity occurred, Fig. 7). This pre-
liminary qualitative test confirmed the efficient anchorage of the
stabilizer and the absence of water pockets (at least distinguish-
able by the naked eye), generally associated with the presence of
low molar mass surfactants. This observation was in good agree-
ment with that of a previous study utilizing polymerizable sur-
factant for the synthesis of latexes used for pressure-sensitive
adhesives [4].

Fig. 6. CryoTEM images of the latex PSSNa- L4 (b) Digital magnification of (a).
 E. Velasquez et al. / Polymer 106 (2016) 275e284
Table 4
Thermal properties of some PMAA and PSSNa-stabilized latexes.
Latex MacroRAFT agent Latex pH MFFT ( C)a
PMAA-L5 PMAA6 6.2 12.0
PSSNa-L1 PSSNa4 2.0 10.3
PSSNa-L2 PSSNa4 2.0 11.2
PSSNa-L4 PSSNa5 1.6 8.9
a
Minimum Film Forming Temperature.
b
Glass transition temperature, Tg2, measured at the second heating.
Fig. 7. Transparent film obtained from Latex PSSNa-L4 after immersion in water for 2 h
at 95  C (black background).
4. Conclusion
Emulsion copolymerization of VDC and MA was performed in
the presence of various hydrophilic macroRAFT agents (PAA, PMAA
and PSSNa) using a one-pot/two-step strategy. The macroRAFT
agents, first synthesized in water, were directly employed in very
low amounts (typically < 2 wt% with respect to the hydrophobic
monomer) to act as transurf during the emulsion polymerization
step. Amphiphilic block copolymers were thus produced in situ,
providing stabilization to the P(VDC-co-MA) particles. PAA-
mediated emulsion copolymerization of VDC and MA led to large
particles (>400 nm) only stable when a high amount of MA (30 mol
%) was used. The lack of stability observed for lower MA amount
was ascribed to a poor efficiency of the chain transfer reaction
negatively impacting the nucleation step. PMAA and PSSNa mac-
roRAFT agents led to a much more efficient chain transfer reaction
in water at the beginning of the copolymerization, and P(VDC-co-
MA) latexes with a composition required for typical applications
(11 mol% of MA) were obtained. Indeed, PMAA-b-P(VDC-co-MA) or
PSSNa-b-P(VDC-co-MA) amphiphilic block copolymers being
formed faster, a more efficient nucleation was thus observed and
much smaller particles (between 136 and 211 nm, and 66 and
93 nm, respectively) were obtained. For both PMAA and PSSNa,
surface tension measurements performed on the corresponding
film-forming latexes showed that a quantitative anchoring of the
macroRAFT agents at the surface of the particles could be achieved.
The absence of hydrophilic species in the serum of the latex
allowed forming transparent films that did not whiten when
immersed in water. In our previous work relying on the use of PEO-
TTC macroRAFT agents, stable PVDC latexes reaching a solids con-
tent of 10 wt% were obtained using 6 wt% of PEO-TTC [16]. The one-
pot strategy presented in this paper leads to significant improve-
ments: to the best of our knowledge, this is the first study reporting
the synthesis of high solids content (40 wt%) and self-stabilized
PVDC latexes using macroRAFT agents and incorporating low
283
amount of hydrophilic species (<2 wt%).
Tg2b ( C) Acknowledgements
17.9
21.4 The authors thank the French Agence Nationale de la Recherche
21.8 (ANR-2010-RMNP-005-02 ASAP) for financial support of this work.
21.2
The authors warmly thank Prof. Bernadette Charleux for her active
s Crepet
participation to this project and fruitful discussions. Agne
(IMP, Villeurbanne) is acknowledged for her assistance in aqueous
SEC of PSSNa samples, Pierre-Yves Dugas (C2P2, Villeurbanne) for
the cryo-TEM analysis.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.polymer.2016.08.083.
References
[1] E. Kientz, Y. Holl, Distribution of surfactants in latex films, Colloids Surf. A
Phys. Eng. Asp. 78 (1993) 255e270.
[2] J.L. Keddie, Film formation of latex, Mater. Sci. Eng. R. 21 (1997) 101e170.
[3] J.L. Keddie, A.F. Routh, Surfactant Distribution in Latex Films. Fundamentals of
Latex Film Formation: Processes and Properties, Springer, Dordrecht
Netherlands, 2010, pp. 185e212.
[4] Z. Aguirreurreta, J.-A. Dimmer, I. Willerich, J.C. de la Cal, J.R. Leiza, Water
whitening reduction in waterborne pressure-sensitive adhesives produced
with polymerizable surfactants, Macromol. Mater. Eng. 300 (2015) 925e936.
[5] Y. Liu, A.M. Gajewicz, V. Rodin, W.-J. Soer, J. Scheerder, G. Satgurunathan,
P.J. McDonald, J.L. Keddie, Explanations for water whitening in secondary
dispersion and emulsion polymer films, J. Polym. Sci. Part B Polym. Phys. 54
(2016) 1658e1674.
[6] R.A. Wessling, D.S. Gibbs, B.E. Obi, D.E. Beyer, P.T. DeLassus, B.A. Howell,
Vinylidene Chloride Polymers. Kirk-Othmer Encyclopedia of Chemical Tech-
nology, fifth ed., vol. 25, John Wiley & Sons, Inc, 2007, pp. 691e745.
[7] D.S. Lee, K.L. Yam, Polyvinylidene chloride (PVDC), in: K.L. Yam (Ed.), The
Wiley Encyclopedia of Packaging Technology, third ed., Wiley, 2010, pp.
1012e1015.
[8] J. Vinas, P.E. Dufils, Poly(Vinylidene chloride), in: Ullmann's Encyclopedia of
Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, 2012.
[9] A. Guyot, K. Tauer, Polymerizable and polymeric surfactants, in: J. Texter (Ed.),
Reactions and Synthesis in Surfactants Systems, vol. 100, Marcel Dekker, New
York, 2001, pp. 547e576. XXVIII.
[10] P.B. Zetterlund, S.C. Thickett, S. Perrier, E. Bourgeat-Lami, M. Lansalot,
Controlled/living radical polymerization in dispersed systems: an update,
Chem. Rev. 115 (2015) 9745e9800.
[11] S.L. Canning, G.N. Smith, S.P. Armes, A critical appraisal of RAFT-mediated
polymerization-induced self-assembly, Macromolecules 49 (2016)
1985e2001.
[12] M. Lansalot, J. Rieger, F. D’Agosto, Polymerization-induced self-assembly: the
contribution of controlled radical polymerization to the formation of self-
stabilized polymer particles of various morphologies, in: Macromolecular
Self-assembly, John Wiley & Sons, Inc., 2016, pp. 33e82.
[13] C.J. Ferguson, R.J. Hughes, D. Nguyen, B.T.T. Pham, R.G. Gilbert, A.K. Serelis,
C.H. Such, B.S. Hawkett, Ab initio emulsion polymerization by RAFT-controlled
self-assembly, Macromolecules 38 (2005) 2191e2204.
[14] I. Chaduc, W. Zhang, J. Rieger, M. Lansalot, F. D'Agosto, B. Charleux, Amphi-
philic block copolymers from a direct and one-pot RAFT synthesis in water,
Macromol. Rapid Commun. 32 (2011) 1270e1276.
[15] M. Chenal, J. Rieger, C. Ve
chambre, J.-M. Chenal, L. Chazeau, C. Creton,
L. Bouteiller, Soft nanostructured films with an ultra-low volume fraction of
percolating hard phase, Macromol. Rapid Commun. 34 (2013) 1524e1529.
[16] E. Velasquez, J. Rieger, F. Stoffelbach, B. Charleux, F. D'Agosto, M. Lansalot, P.-
E. Dufils, J. Vinas, Study of the solution and aqueous emulsion copolymeri-
zation of vinylidene chloride with methyl acrylate in the presence a poly(-
ethylene oxide) macromolecular RAFT agent, Polymer 54 (2013) 6547e6554.
[17] J. Yang, Y. Bao, P. Pan, Ab initio emulsion RAFT polymerization of vinylidene
chloride mediated by amphiphilic macro-RAFT agents, J. Appl. Polym. Sci. 131
(2014), http://dx.doi.org/10.1002/APP.40391.
[18] M. Manguian, M. Save, B. Charleux, Batch emulsion polymerization of styrene
stabilized by a hydrophilic macro-RAFT agent, Macromol. Rapid Commun. 27
(2006) 399e404.
[19] A.M. Dos Santos, J. Pohn, M. Lansalot, F. D'Agosto, Combining steric and
electrostatic stabilization using hydrophilic macroRAFT agents in an ab initio
emulsion polymerization of styrene, Macromol. Rapid Commun. 28 (2007)
1325e1332.
[20] J. Bernard, M. Save, B. Arathoon, B. Charleux, Preparation of a xanthate-
terminated dextran by click chemistry: application to the synthesis of
polysaccharide-coated nanoparticles via surfactant-free ab initio emulsion
284 E. Velasquez et al. / Polymer 106 (2016) 275e284
polymerization of vinyl acetate, J. Polym. Sci. Part A Polym. Chem. 46 (2008)
2845e2857.
[21] T. Boursier, I. Chaduc, J. Rieger, F. D'Agosto, M. Lansalot, B. Charleux,
Controlled radical polymerization of styrene in miniemulsion mediated by
PEO-based trithiocarbonate macromolecular RAFT agents, Polym. Chem. 2
(2011) 355e362.
[22] H. Thielking, W.-M. Kulicke, On-line coupling of flow field-flow fractionation
and multiangle laser light scattering for the characterization of macromole-
cules in aqueous solution as illustrated by sulfonated polystyrene samples,
Anal. Chem. 68 (1996) 1169e1173.
[23] I. Chaduc, A. Crepet, O. Boyron, B. Charleux, F. D'Agosto, M. Lansalot, Effect of
the pH on the RAFT polymerization of acrylic acid in water. Application to the
synthesis of poly(acrylic acid)-stabilized polystyrene particles by RAFT
emulsion polymerization, Macromolecules 46 (2013) 6013e6023.
[24] I. Chaduc, M. Girod, R. Antoine, B. Charleux, F. D'Agosto, M. Lansalot, Batch
emulsion polymerization mediated by poly(methacrylic acid) macroRAFT
agents: one-pot synthesis of self-stabilized particles, Macromolecules 45
(2012) 5881e5893.
[25] I. Chaduc, M. Lansalot, F. D'Agosto, B. Charleux, RAFT polymerization of
methacrylic acid in water, Macromolecules 45 (2012) 1241e1247.
[26] J. Chiefari, B.Y.K. Chong, F. Ercole, J. Krstina, J. Jeffery, T.P.T. Le,
R.T.A. Mayadunne, G.F. Meijs, C.L. Moad, G. Moad, E. Rizzardo, S. Thang, Living
free-radical polymerization by reversible addition-fragmentation chain
transfer: the RAFT process, Macromolecules 31 (1998) 5559e5562.
[27] Y. Mitsukami, M.S. Donovan, A.B. Lowe, C.L. McCormick, Water-soluble poly-
mers. 81. Direct synthesis of hydrophilic styrenic-based homopolymers and
block copolymers in aqueous solution via RAFT, Macromolecules 34 (2001)
2248e2256.
[28] M. Mertoglu, S. Garnier, A. Laschewsky, K. Skrabania, J. Storsberg, Stimuli
responsive amphiphilic block copolymers for aqueous media synthesised via
reversible addition fragmentation chain transfer polymerisation (RAFT),
Polymer 46 (2005) 7726e7740.
[29] M. Mertoglu, A. Laschewsky, K. Skrabania, C. Wieland, New water soluble
agents for reversible addition
fragmentation chain transfer polymerization
and their application in aqueous solutions, Macromolecules 38 (2005)
3601e3614.
[30] N. Yeole, D. Hundiwale, Effect of hydrophilic macro-RAFT agent in surfactant-
free emulsion polymerization, Colloids Surf. A Phys. Eng. Asp. 392 (2011)
329e334.
[31] N. Yeole, D. Hundiwale, T. Jana, Synthesis of core-shell polystyrene
nanoparticles by surfactant free emulsion polymerization using macro-RAFT
agent, J. Colloid Interface Sci. 354 (2011) 506e510.
[32] N. Yeole, D. Hundiwale, Effect of Varying Hydrophobic Monomers and Their
Copolymerization in Surfactant-Free Emulsion Polymerizations Using a
Macro-RAFT Agent, vol. 3, RSC Adv, 2013, pp. 22213e22218.
[33] M. Barsbay, O. Güven, T.P. Davis, C. Barner-Kowollik, L. Barner, RAFT-mediated
polymerization and grafting of sodium 4-styrenesulfonate from cellulose
initiated via g-radiation, Polymer 50 (2009) 973e982.
[34] F.R. Mayo, F.M. Lewis, C. Walling, Copolymerization VIII. The relation between
structure and reactivity of monomers in copolymerization1, J. Am. Chem. Soc.
70 (1948) 1529e1533.
[35] S. Collins, K. Yoda, N. Anazawa, C. Birkinshaw, The thermal stability of some
vinylidene chloride copolymers, Polym. Degrad. Stab. 66 (1999) 87e94.
[36] G.H.J. van Doremaele, F.H.J.M. Geerts, H.A.S. Schoonbrood, J. Kurja,
A.L. German, Effect of composition drift on emulsion copolymerization rate,
Polymer 33 (1992) 1914e1921.
[37] S. Nozari, K. Tauer, A.I. Ali, RAFT agent concentration in polymer particles
during emulsion polymerization, Macromolecules 38 (2005) 10449.
[38] Y. Luo, X. Wang, B.-G. Li, S. Zhu, Toward well-controlled ab initio RAFT
emulsion polymerization of styrene mediated by 2-(((Dodecylsulfanyl)car-
bonothioyl)sulfanyl)propanoic acid, Macromolecules 44 (2011) 221e229.
[39] J. Brandrup, E.H. Immergut, E.A. Grulke, A. Abe, D.R. Bloch, Polymer Handbook,
fourth ed., John Wiley and Sons, Inc., 1999, p. II/68.
[40] J. Brandrup, E.H. Immergut, E.A. Grulke, A. Abe, D.R. Bloch, Polymer Handbook,
fourth ed., John Wiley and Sons, Inc., 1999, p. II/6.
[41] The measured pKa value for a similar PAA macroRAFT agent with a thio-
dodecyl Z group instead of a thiopropyl one (Mn,exp ¼ 2400 g mol-1) was 5.7
(data not shown).
[42] M. Chenal, L. Bouteiller, J. Rieger, Ab initio RAFT emulsion polymerization of
butyl acrylate mediated by poly(acrylic acid) trithiocarbonate, Polym. Chem. 4
(2013) 752e762.
[43] E. Velasquez, G. Pembouong, J. Rieger, F. Stoffelbach, O. Boyron, B. Charleux,
F. D'Agosto, M. Lansalot, P.-E. Dufils, J. Vinas, Poly(vinylidene chloride)-based
amphiphilic block copolymers, Macromolecules 46 (2013) 664e673.
[44] R. Severac, P. Lacroix-Desmazes, B. Boutevin, Reversible addition-
fragmentation chain-transfer (RAFT) copolymerization of vinylidene chlo-
ride and methyl acrylate, Polym. Int. 51 (2002) 1117e1122.
[45] The measured pKa value for the PMAA4 macroRAFT agent was 5.9 (data not
shown).