Article

Cite This: Ind. Eng. Chem. Res. 2019, 58, 8140−8147 pubs.acs.org/IECR

Tailoring Emulsion Polymerization for High-Yield Synthesis of

Tween 80 Stabilized Magnetic Cross-Linked Polystyrene
Nanocomposite Particles
Xiaojing Liu and Yangcheng Lu*
State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing100084, China
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Tween 80 coated magnetic polymer nano-

composite particles (NCPs), as functional materials with good
biological application prospects, still confront a challenge in
Downloaded via KAROLINSKA INST on February 28, 2020 at 21:11:08 (UTC).

high-yield preparation inhibiting either plain polymer particles

or aggregates. In this study, we are devoted to make a
breakthrough by using emulsion polymerization solely
stabilized by nonionic surfactant Tween 80 and initiated by
an oil-soluble initiator, 2,2′-azobis(isobutyronitrile). After
carefully investigating the effects of Fe3O4, monomer, initiator,
and emulsifier dosages on the monomer conversion,
encapsulation efficiency, and particle characteristics, we
confirm that a low but sufficient Tween 80 dosage relative
to the Fe3O4 dosage enables the high-yield synthesis of NCPs.
Using a micromixing method to prepare colloidal Fe3O4 clusters at the reduced Tween 80 concentration allows for the
production of monodispersed NCPs with considerable monomer conversion and total encapsulation. The mechanism to
achieve controlled NCPs synthesis is also revealed by monitoring and analyzing the time profiles of monomer conversion and
products morphology.

1. INTRODUCTION steric interaction due to the presence of oligomoieties and

Magnetic polymer nanocomposite particles (NCPs) are of
increasing interest in both academia and industry.1,2 The
marriage of magnetically responsive particles (usually Fe3O4)
and various kinds of polymers opens pathways to various
applications. For example, in the biomedical field, the polymer
shell, encapsulating a cluster of magnetic nanoparticles
(MNPs), can prevent them from oxidation and direct contact
with other components like biomolecules and also can be
functionalized by bioactive molecules and ligands. It endows
the NCPs with extensive biomedical applications,3−6 from
contrast agents of magnetic resonance imaging to drug
delivery, catalysis,7,8 and separation.9,10
The emulsion polymerization is an important method for
the commercial production of NCPs.1 Most of the reported
works relied on the conventional emulsion polymerization
processes with colloidal iron oxide clusters as magnetic
seeds.11,12 A high-quality magnetic polymer latex usually
requires that all the particles have uniform properties in
terms of particle size, magnetite loading, etc. To this end, the
synthesis of NCPs needs the production of finely dispersed
magnetite clusters in dispersion medium at the initial stage and
maintenance of colloidal stability during polymerization.13
The emulsifier is a crucial influence factor for the stability of
the polymerization process.14,15 PEG-based polyoxyethylene
(80) sorbitan monolaurate (Tween 80) is an effective nonionic
surfactant providing high stability for colloidal nanocrystals by
hydroxyl groups on the headgroup.16−18 Besides, Tween 80
can remarkably weaken the bioadhesion between biotissues
and biomedical devices,19 which endows the Tween 80 coated
polymer nanoparticles with good biocompatibility and
potentiality in biological applications, such as the delivery of
various drugs through the blood-brain barrier to achieve a
significant pharmacological effect.20−22 However, it is rare to
use the nonionic emulsifier like Tween 80 solely in
conventional emulsion polymerization using a water-soluble
initiator like persulfate because of low monomer conversion
and poor particle size distribution (PSD).23 An explanation is
that the incorporation of charged groups coming from water-
soluble initiator decomposition onto the particle surface could
decrease the amount of adsorbed emulsifier and cause the
particle destabilization during polymerization.14 Alternatively,
Weiss et al.24 reported that the Tween 80 stabilized
monodispersed particles could be obtained by using a nonionic
initiator, 2,2′-azo-bis[2-methyl-N-(2-hydroxyethyl)-
propionamide]. Indeed, the nonionic initiators have been
more frequently used in emulsion polymerization in recent
years.24,25
Received: February 26, 2019
Revised: April 24, 2019
Accepted: April 30, 2019
Published: April 30, 2019

© 2019 American Chemical Society 8140 DOI: 10.1021/acs.iecr.9b01103

Ind. Eng. Chem. Res. 2019, 58, 8140−8147
Industrial & Engineering Chemistry Research Article

The exclusive synthesis of composite particles (encapsula- oxygen for at least 1 h before using. Other reagents were used
tion efficiency 100%, without plain polymer particles)26,27 is as-received.
fundamental to guarantee the uniformity in constituents of 2.2. Preparation of OA-Modified Fe3O4 Nanoparticles.
each NCP as well as control and customize their application Fe3O4 nanoparticles were synthesized by the coprecipitation
performance. However, to our knowledge, there are few method.30,31 That is, 0.486 g of FeCl3 and 0.299 g of FeCl2·
reports about magnetic NCPs preparation that focused on the 4H2O were dissolved in 45 mL of water, and then 4 mL of a 5
improvement of both monomer conversion and encapsulation M ammonium hydroxide was added quickly to the solution
efficiency. Xu et al.28 synthesized monodisperse super- under nitrogen atmosphere with mechanical stirring (700
paramagnetic colloid particles for magnetically controllable rpm). After 20 min of the coprecipitation reaction at room
photonic crystals and found that only around 3.5 wt % of the temperature, 0.28 mL of oleic acid was added dropwise into
polystyrene particles contained iron oxide particles. Cui et al.29 the aqueous iron oxide suspension. The resulting mixture was
developed a hybrid emulsion polymerization system to heated to 80 °C to evaporate the ammonia gradually until the
synthesize Fe3O4/polystyrene with high magnetite content, Fe3O4 was precipitated from solution. Finally, the black
but the monomer conversion was lower than 20 wt %. Wu et precipitation was washed with water and acetone three times
al.26 carefully adjusted the impact factors of the polymerization separately to remove ions and excessive oleic acid. The
procedure and obtained magnetic polymer nanoparticles with obtained nanoparticles were dispersed in THF with a solid
high monomer conversion of 83%, but the gravimetric method content of 20 mg/mL for further use.
they used was unable to get rid of the plain polymer 2.3. Preparation of Colloidal Fe3O4 Clusters. Tween 80
nanospheres adhered to NCPs (easily observed in TEM and THF were first added to the Fe3O4-THF magnetic
photos) and may result in some overestimation of conversion. suspension prepared in section 2.2 according to the formulas in
All in all, it is still a challenge for high yield synthesis of Table 1. The as-prepared Fe3O4-Tween 80-THF magnetic
uniform NCPs through a precisely controlled emulsion
polymerization. Table 1. Formulas of the Colloidal Fe3O4 Clusters
In this work, using oil-soluble 2,2′-azobis(isobutyronitrile)
magnetic suspension
(AIBN) as initiator and Tween 80 as emulsifier, we carried out
the preparations of Tween 80 coated Fe3O4-poly(styrene-co- Fe3O4 THF Fe3O4 Tween 80 water cluster size
clusters (mL) (mg) (mg) (mL) (nm)
divinylbenzene) NCPs via emulsion polymerization at various
recipes. Systematical characterizations on monomer conversion MC1a 10 30 200 40 64.4 ± 2.5
and the morphology and encapsulation efficiency of products MC2a 10 100 200 40 104.6 ± 5.2
were carefully conducted to investigate the polymerization MC3a 10 150 200 40 135.9 ± 6.6
characterization of the Tween 80 solely stabilized emulsion MC4b 10 30 10 40 43.9 ± 0.7
system in the presence of inorganic particles. The influential MC5b 10 100 10 40 68.1 ± 1.3
a b
effects of the concentration of Tween 80 on both Preparation via the bulk-dripping method. Preparation via the
encapsulation efficiency and the polymerization rate were micromixing method.
revealed and discussed based on species distribution. Through
controlling the dosage of Tween 80 at low level by preparing suspension and pure water were mixed by two different mixing
stable Fe3O4 clusters aqueous suspension with low addition of methods. The first method was the bulk-dripping method, i.e.,
Tween 80 via a micromixing method, we eliminated the vacant 10 mL of magnetic suspension was injected into a mechanically
micelles effectively in the emulsion system that cause low stirred (700 rpm) pure water solution (40 mL) dropwise via
encapsulation efficiency and monomer conversion and syringe pump at a rate of 1 mL/min. The second method was
obtained high-yield monodispersed (PDI = 0.068) NCPs the micromixing method using a stainless steel T-junction as
successfully. In addition, based on the study of morphology micromixer (inner diameter, 0.25 mm). Two syringe pumps
and composition evolution of products, we further clarified the (TS-1B/W0109-1B, Longer, China) pumped 10 mL of the
course and mechanism of a controlled NCPs synthesis, magnetic suspension and 40 mL of pure water simultaneously
providing theoretical and methodological fundamentals for into the micromixer to start shearing-mixing. The flow rates of
the preparation of NCPs with high quality. magnetic fluid and water were 5 mL/min and 20 mL/min,
respectively. After mixing, the mixtures were collected and
2. MATERIALS AND METHODS transferred into a rotary evaporator to remove THF. Extra pure
2.1. Materials. Iron(III) chloride anhydrous (FeCl3) and water was added according to the experimental conditions
oleic acid were obtained from Alfa Aesar (UK). Iron(II) shown in Table 2.
chloride tetrahydrate (FeCl2·4H2O) was obtained from 2.4. Preparation of Magnetic Cross-Linked Polystyr-
Aladdin (China). HPLC grade tetrahydrofuran (THF) was ene NCPs. The colloidal Fe3O4 clusters were transferred into a
obtained from Fisher Chemical (USA). Tween 80, acetone, three-necked flask and stripped with nitrogen to remove
ammonium hydroxide (28 wt %), sodium hydroxide (NaOH), dissolved oxygen for 30 min. St, DVB, and AIBN were mixed
and styrene (St) were obtained from Sinopharm (China). at various ratios (Table 2) and added dropwise into the Fe3O4
Divinylbenzene (DVB) was obtained from J&K (China). The cluster suspension under stirring (700 rpm) for 60 min, and
water used throughout the experiments was ultrapure water then, the flask was placed in a thermostat at 70 °C to start up
produced from a water purification machine (Center 120FV- polymerization. As the preset reaction time was reached, the
S). Styrene and divinylbenzene were washed with 5 wt % of polymerization was quenched by submerging the reaction flask
NaOH and water sequentially to remove the polymerization into an ice bath. The product was filtered out and washed with
inhibitors and then purified by distillation under reduced water three times.
pressure. AIBN was recrystallized twice from ethanol. Besides, 2.5. Characterization. The morphology of particles,
St and water were stripped with nitrogen to remove dissolved including the Fe3O4 nanoparticles, nanoclusters, and NCPs,
8141 DOI: 10.1021/acs.iecr.9b01103
Ind. Eng. Chem. Res. 2019, 58, 8140−8147
Industrial & Engineering Chemistry Research Article

Table 2. Summary on Experimental Conditions and Results of Polymerizationa

monomer (μL)
Latex clusters Fe3O4 (mg) Tween (mg) St DVB AIBN (mg) conversion (%) EE (%) magnetization (emu/g)b
1 MC1 30 200 900 600 15 92.5 ± 3.2 22.6 ± 0.6 4.2
2 MC2 100 200 900 600 15 49.3 ± 0.7 49.9 ± 2.3 14.6
3 MC3 150 200 900 600 15 37.6 ± 1.1 61.7 ± 0.6 19.1
4 MC1 30 200 450 300 7.5 29.8 ± 1.2 67.5 ± 3.3 8.9
5 MC1 30 200 300 200 5 13.6 ± 0.4 100 17.3
6 MC1 30 200 300 200 15 64.7 ± 0.9 23.7 ± 0.9 15.7
7 MC2 100 200 300 200 15 45.5 ± 1.6 40.2 ± 1.8 15.5
8 MC4 30 10 300 200 15 50.4 ± 1.2 100 8.3
9 MC5 100 10 300 200 15 78.2 ± 0.7 81.8 ± 3.7 14.6
10 MC5 100 13 300 200 15 70.1 ± 0.9 100 12.7
a
The content of water is 40 mL for all experimental conditions. bSaturation magnetization at room temperature.

was observed by using a transmission electron microscope
(TEM) instrument (JEM 2010, JEOL, Japan). The thermog-
ravimetric analysis (TGA) was carried out by using STA 409
PC (NETZSCH, Germany), with a heating rate of 10 °C/min
and nitrogen flow at a rate of 20 mL/min. The size distribution
was characterized by dynamic light scattering (DLS, SZ-100,
HORIBA, Japan). The vibrating sample magnetometry (VSM;
SQUID-VSM, Quantum Design, USA) was used to analyze the
magnetic properties of the obtained NCPs under dry
conditions.
The monomer conversion was measured with the gravi-
metric method. In detail, a certain amount of latex was taken
after polymerization, precipitated by alcohol, and then dried at
60 °C in a vacuum oven for 12 h. The monomer conversion
was calculated by eq 1
m2
m1
× m T − mF
C= × 100%
mM
where m1, m2, mT, mF, and mM correspond to the mass of latex
sample, dried latex sample, the whole latex, the added Fe3O4
nanoparticles, and the added monomer, respectively. The
encapsulation efficiency (EE) was also measured with the
gravimetric method. A certain amount of latex sample was
placed in a Petri dish with a diameter of 9 cm above a square
magnet (6 × 6 cm2). After 10 min, the brown solid latex was
magnetically separated to the bottom of the Petri dish, which
was considered the magnetic NCPs, and the upper latex that
still dispersed in aqueous phase was then transferred to a
centrifuge tube by using aspirating pipets, which was regarded
as the plain polymer particles. The two kinds of latexes were
respectively precipitated by alcohol and then dried at 60 °C in
a vacuum oven for 12 h. The value of EE can be calculated
using eq 2
m m − m1mF
EE = 3 T × 100%
m2m T − m1mF (2)
where m3 corresponds to the mass of dried magnetic NCPs.
3. RESULTS AND DISCUSSION
3.1. General Characteristics of NCPs Synthesis with
Constant Emulsifier Addition. The synthesis of NCPs
consists of the formation of Tween 80 stabilized colloidal
Fe3O4 clusters and then the polymer shell. As for the
preparation of Fe3O4 clusters, the hydrophobic Fe3O4 particles
were transferred into water as clusters with the assistance of
Tween 80, forming the Fe3O4-containing micelles. The
colloidal assembly induced by the mixing of the Fe3O4-
Tween 80-THF magnetite suspension and pure water just
abides the solvent-exchange mechanism,32,33 and the mean size
of the clusters generally increased with the increase of the
Fe3O4 amount, as shown in Figure S1 of the Supporting
Information and Table 1. The surfactant bilayers on the surface
of clusters, consisting of the hydrophobic ligands on the Fe3O4
nanoparticles and the hydrophobic part of the Tween 80, could
improve the solubilization of the monomer and initiator in the
hydrophobic interlayer, which provides effective loci for free
radical polymerization to realize the formation of the polymer
shell as well as the final NCPs. For an ideal scenario, all
monomer molecules added into the reaction system should
polymerize on the surface of Fe3O4 clusters. To this end, we
first fixed the addition of emulsifier at 200 mg and made trials
by changing the dosages of the monomer and Fe3O4 carefully.
When the dosages of the monomer and Fe3O4 were 1500 μL
and 30 mg, respectively (Latex 1 in Table 2), Fe3O4 clusters
(1)
were encapsulated into the polymer shell to generate spherical
NCPs (Figure 1(a)). The monomer conversion after 3.5 h was
Figure 1. TEM images of NCPs and plain polymer particles prepared
with different monomers and AIBN doses. (a, b) Latex 1, (c) Latex 4,
(d) Latex 5. Polymerization time, 3.5 h. T = 70 °C.
92.5%, but only 22.6% of the polymerized monomer formed
on the surface of Fe3O4 clusters, indicating that there existed a
large amount of plain polymer particles. These undesired
particles are far smaller in size than NCPs, as shown in Figure
1(b). Taking Latex 1 as a control group, as decreasing the
dosages of monomer and initiator proportionally (Latexes 4
8142 DOI: 10.1021/acs.iecr.9b01103
Ind. Eng. Chem. Res. 2019, 58, 8140−8147
Industrial & Engineering Chemistry Research
and 5), the encapsulation efficiency increased remarkably, but
the monomer conversion decreased sharply. Correspondingly,
the products could not keep their morphology in spherical
shape (Figure 1(c) and Figure 1(d)) due to the low ratio of
polymer to Fe3O4 clusters. As individually increasing the
addition of Fe3O4 from 30 mg (Latex 1) to 100 mg (Latex 2)
and 150 mg (Latex 3), the number of Fe3O4 nanoparticles
embedded in each NCP increased (Figure 2(a) and Figure
Figure 2. TEM images of NCPs prepared with different Fe3O4
dosages. (a) Latex 2, (b) Latex 3. Polymerization time, 3.5 h. T =
70 °C.
2(b)), which may enhance the magnetic response on an
external magnetic field. Meanwhile, the encapsulation
efficiency increased from 22.6% to 49.9% and 61.7%,
respectively; the total monomer conversion decreased from
92.5% to 49.3% and 37.6%, respectively. There still exists a
trade-off between encapsulation efficiency and monomer
conversion.
The wide existence of plain polymer nanoparticles in Latex 1
indicates that many Tween 80 molecules were not distributed
on the surface of Fe3O4 clusters during emulsion polymer-
ization. Even if the dosage of Fe3O4 increases 5 times to 150
mg (Latex 3), this situation does not change. As a result, except
for the Fe3O4-containing micelles, there also exist many vacant
micelles in these reaction systems. So, the monomer droplets
could supply a monomer to both of these two kinds of
micelles, forming different monomer swelling micelles. The oil-
soluble AIBN molecules that are distributed in monomer
swelling Fe3O4-containing micelles decomposed and sub-
sequently initiated the polymerization of the monomer on
the surface of Fe3O4 clusters, while the AIBN distributed in
monomer swelling vacant micelles can lead to the generation of
plain polymer particles. A reduced amount of the monomer or
AIBN in micelles can slow down the synthesis rate of
corresponding particles. To reduce the plain polymer particles,
a strategy is to distribute the monomer or AIBN in Fe3O4-
containing micelles rather than in vacant micelles. The increase
of encapsulation efficiency with the decrease of monomer and
AIBN dosages in proportion, derived from the comparison of
Latexes 1, 4, and 5, indicates that the proportion of AIBN
distributed in vacant micelles decreased correspondingly.
AIBN seems to prefer to distribute into the Fe3O4-containing
micelles until its addition exceeds a threshold value. This
inference can also be supported by the comparison of Latex 6
(Figure 3(a)) and Latex 5 (Figure 1(d)), which shows that the
individual increase of the AIBN dosage from 5 mg to 15 mg
leads to a decrease of encapsulation efficiency from 100% to
23.7%. The excessive AIBN could enter into the vacant
micelles and accelerate the polymerization in vacant micelles.
On the other hand, when decreasing the AIBN dosage, the
amount of AIBN molecules in vacant micelles decreases, and
the polymerization of the monomer in vacant micelles can slow
down due to the lack of AIBN. It may result in the decrease of
8143
Article
Figure 3. TEM images of NCPs prepared with different polymer-
ization conditions. (a) Latex 6, (b) Latex 7. Polymerization time, 3.5
h. T = 70 °C.
the proportion of plain polymer particles in the final products
as well as the decrease of the polymerization rate. In keeping
the dosage of AIBN but increasing the Fe3O4 dosage, the
number of Fe3O4-containing micelles will increase and capture
more AIBN, which is favorable for increasing the encapsulation
efficiency but unfavorable for the polymerization in the vacant
micelles, as compared to what the comparisons of Latex 1, 2,
and 3 show. When comparing Latex 7 (Figure 3(b)) with
Latex 2 (Latex 2(a)), which have the same dosage of AIBN
and different amounts of the monomer (1500 and 500 μL), we
could find that the encapsulation efficiency almost remained
constant, as shown in Table 2. It indicates that the distribution
of the monomer between Fe3O4-containing micelles and
vacant micelles is almost independent of its dosage.
In general, it can be concluded that the plain polymer
nanoparticles are the results of vacant monomer swelling
micelles and the dissolved AIBN inside. The monomer
molecules can diffuse into any kind of micelle during emulsion
polymerization, while the AIBN molecules demonstrate a
preferential distribution in Fe3O4-containing micelles. Increas-
ing the Fe3O4 dosage or reducing the AIBN dosage can help to
inhibit the formation of plain polymer particles by decreasing
the dissolved AIBN in vacant micelles. It is totally possible to
realize 100% of encapsulation efficiency when the mass ratio of
AIBN-to-Fe3O4 is low enough to avoid the existence of AIBN
in vacant micelles. However, the polymerization rate may be
very low once the monomer solubilized in vacant micelles is
considerable and trapped inside by the complex molecular
structure of Tween 80, since the mass transfer of monomer
molecules between micelles is truly slow.34 So, it is hard to
realize efficient NCP preparation by simply adjusting the
dosages of Fe3O4, monomer, and initiator in the presence of
vacant micelles.
3.2. Enhancing NCPs Synthesis by Decreasing
Emulsifier Addition. Availability To Synthesize NCPs with
High Conversion and High Encapsulation Efficiency. Since
the presence of vacant micelles corresponds to an excessive
emulsifier addition, we tried to decrease the emulsifier addition
in the reaction system for NCPs preparation, looking forward
to increasing both encapsulation efficiency and the polymer-
ization rate. However, when we simply decreased the dosage of
Tween 80 further in the preparation of colloidal Fe3O4 clusters
via the bulk-dripping method, large-sized cluster aggregations
could be observed and continuously precipitated to the bottom
of the flask, indicating poor stability. It has been widely known
that the bulk-dripping could not provide fast and controlled
mixing,35 so the decrement Tween 80 cannot reach the surface
of Fe3O4 nanoparticles promptly to prevent the generation of
large-sized aggregations. Alternatively, using micromixers is a
promising approach to realize the control over the morphology
and size of the assembled structures since it can mix reagents
DOI: 10.1021/acs.iecr.9b01103
Ind. Eng. Chem. Res. 2019, 58, 8140−8147
Industrial & Engineering Chemistry Research
rapidly and provide a uniform assembly environment.36,37 So
in this study, a micromixing method was employed by mixing
THF magnetic suspension with water in a microchannel,
speeding up the transfer rate of Tween 80 molecules.
Promisingly, it was found that only 10 mg of Tween 80 was
needed to stabilize 100 mg of Fe3O4 in 40 mL of water using
this method. In the preparation of Latex 8, when the Tween 80
addition decreased to 10 mg, the monomer conversion and
encapsulation efficiency reached 50.4% and 100%, respectively.
In other words, all products in the emulsion system could be
separated from aqueous phase by an external magnetic field,
and the yield of desired products was improved significantly.
Besides, the diameter and the number of embedded Fe3O4
nanoparticles of each NCP in Latex 8 (Figure 4(a)) were
Figure 4. TEM images of NCPs prepared with relatively low dosages
of Tween 80. (a) Latex 8, (b) Latex 9, (c, d) Latex 10. Polymerization
time, 3.5 h. T = 70 °C.
smaller than that of Latex 6 (Figure 3(a)). The plain polymer
particles were eliminated due to low Tween 80 dosage in the
polymerization system, and almost all Tween 80 molecules
were used for stabilizing the Fe3O4 clusters and monomer
droplets. Even though there may be still some amount of free
Tween 80 dissolved in aqueous phase, this part of Tween 80
was too little to form new micelles and might take effect to
stabilize the enlarged NCPs during the polymerization process.
However, by fixing the emulsifier addition and further
increasing the Fe3O4 addition from 30 mg to 100 mg (Latex
9), the obtained products were found to have large-sized
agglomeration, and around 12.8% of the polymerized
monomer stuck to the stirring blade. This indicates that
Tween 80 is insufficient for stabilizing growing NCPs during
polymerization. Except for these large-sized aggregations, all
products in the latex system could be collected by an external
magnetic field as individually dispersed NPCs with Fe3O4
nanoparticles distributing uniformly in them and without plain
polymer particles attachment, as shown in Figure 4(b). In
order to improve the emulsion stability and eliminate the large-
sized aggregations, the Tween 80 addition was slightly
increased from 10 mg to 13 mg during the preparation of
Latex 10 by postadding 3 mg of Tween 80 into the colloidal
Fe3O4 clusters MC5 (Table 1). The aggregate was successfully
eliminated, and the monomer conversion and encapsulation
efficiency reached 70.1% and 100%, respectively. TEM images
in Figure 4(c) and Figure 4(d) show that the plain polymer
particle could not be observed in the field of vision as well. It
was also found that the monomer conversion using 100 mg of
8144
Article
Fe3O4 (70.1%) is higher than that using 30 mg of Fe3O4
(50.4%). This was attributed to the increased polymerization
loci derived from the increase of Fe3O4 clusters in numbers. In
summary, the fast micromixing method allows for more flexible
control over the dosage of Tween 80 for preparation of stable
Fe3O4 clusters suspension, and almost all Tween 80 molecules
can be distributed on the surface of Fe3O4 clusters, eliminating
the existence of vacant micelles. As a result, high-yield
synthesis of monodispersed (PDI = 0.068) NCPs can be
realized after careful adjustment of polymerization conditions.
Course and Mechanism of Controlled NCPs Synthesis.
The morphology evolution of Latex 10 with polymerization
time was investigated by TEM characterization for the study of
NCPs formation mechanism. In Figure 5(a), corresponding to
Figure 5. TEM images and TGA results (d) of NPCs obtained under
different polymerization times and monomer conversions: (a) 0.5 h,
2%; (b) 1 h, 19%; and (c) 1.5 h, 44%. T = 70 °C. Other
polymerization conditions were the same with Latex 10.
the polymerization time of 30 min and monomer conversion of
2%, we could observe almost bare Fe3O4 clusters coated with
small amounts of polymer. As the polymerization proceeded
for 60 min, a thin polymer shell appears on the surface of
clusters (Figure 5(b)), but these particles incline to stick
together, showing opaque contours because of the low
conversion of 19%. After 90 min of polymerization, the
polymer shell on the cluster surface gets thicker as the
conversion increased to 44%, and well-shaped spheres with
well dispersity were obtained (Figure 5(c)). Extending the
polymerization time to 3.5 h, the particles become almost
monodispersed with a thick polymer shell. As shown in Figure
5(d), the proportion of the polymer shell in NCPs increased as
the polymerization goes on, and the specific values were
consistent with the monomer conversion calculated by the
gravimetric method. These results indicate that the polymer-
ization starts from Fe3O4-containing micelles and proceeds
only on the surface of clusters, increasing the proportion of
shell polymer content in NCPs gradually. The number of
embedded Fe3O4 nanoparticles in one NCP depends on the
number of Fe3O4 particles in the initial cluster, while the
polymer mass proportion of NCPs can be easily adjusted by
the amount of monomer consumed. On the other hand, this
mechanism implies that extending the reaction duration could
improve the monomer conversion further with the guarantee
of around 100% encapsulation efficiency.
DOI: 10.1021/acs.iecr.9b01103
Ind. Eng. Chem. Res. 2019, 58, 8140−8147
Industrial & Engineering Chemistry Research
Figure 6. Proposed polymerization courses under different doses of Tween 80.
For the preparation of magnetic NCPs by emulsion
polymerization stabilized by Tween 80, the precise control
over the Tween 80 dosage is the key factor in achieving high
encapsulation efficiency and high monomer conversion
simultaneously within several hours. As shown in Figure
6(a), under over dosage of Tween 80, both Fe3O4-containing
micelles and vacant micelles exist in cluster suspension (a-1).
After the monomer addition and emulsification process (a-2), a
part of the monomer swells into two kinds of micelles, and the
other is in monomer droplets. AIBN tends to be distributed
into the Fe3O4-containing micelles preferentially, and the
proportion of plain particles among all products increases with
the increase of AIBN dosage since the excessive AIBN has the
opportunity to enter into vacant micelles. However, under a
proper dosage of Tween 80 (Figure 6(b)), almost all Tween 80
molecules distribute on the surface of Fe3O4 clusters,
eliminating the formation of vacant micelles as well as the
plain polymer particles. Monomer molecules gradually transfer
from monomer droplets into the Fe3O4-containing micelles
until their complete consumption. The polymerization rate
increases as the number of Fe3O4 clusters increases in the
emulsion system. The concentration of Tween 80 should also
be carefully adjusted according to the contents of Fe3O4 and
the monomer, since under insufficient dosage of Tween 80
(Figure 6(c)), the destabilization of the emulsion system will
result in the formation of undesired large-sized aggregations.
All these results are based on the oil-soluble initiator, since the
8145
Article
homogeneous nucleation may happen in water-soluble
initiated emulsion polymerization, forming plain polymer
particles even though there is no new micelle formed during
polymerization.
Compared to other researchers’ work, this work realized
precise control over the Tween 80 distribution in the
polymerization system during the preparation stage of colloidal
Fe3O4 clusters via a micromixing method, avoiding any high
energy-consuming treatment like strong shear forces or
ultrasonication, and complex postprocessing for removing the
vacant micelles in aqueous phase. Higher monomer conversion
within several hours is available by increasing the concen-
tration number of Fe3O4 clusters in the emulsion system with
precise control over the Tween 80 amount on the basis of
eliminating the vacant micelles and stabilizing the emulsion
system.
4. CONCLUSION
In this study, Tween 80 coated magnetic poly(styrene-co-
divinylbenzene) nanocomposite particles were efficiently
prepared using AIBN initiated emulsion polymerization. The
effects of Fe3O4, monomer, initiator, and emulsifier dosages on
the monomer conversion, encapsulation efficiency, and particle
characteristics were carefully investigated. It was found that the
plain polymer nanoparticles originated from vacant monomer
swelling micelles with dissolved AIBN inside. When there exist
vacant micelles in emulsion systems, the monomer molecules
DOI: 10.1021/acs.iecr.9b01103
Ind. Eng. Chem. Res. 2019, 58, 8140−8147
Industrial & Engineering Chemistry Research
can diffuse into both Fe3O4-containing micelles and vacant
micelles without priority; the AIBN molecules demonstrate a
preferential distribution in Fe3O4-containing micelles first, and
the remainder is then distributed in the vacant micelles.
Reducing the ratio of AIBN-to-Fe3O4 can inhibit the formation
of plain polymer particles by decreasing the dissolved AIBN in
vacant micelles. It is totally possible to realize 100% of
encapsulation efficiency, but the monomer trapped in vacant
micelles can lead to the low monomer conversion. In
comparison, elimination of vacant micelles, practicable by
precise control of Tween 80 concentration in the emulsion
system through a fast micromixing method during the
preparation of colloidal Fe3O4 clusters, can help to achieve
high monomer conversion with the guarantee of around 100%
encapsulation efficiency through several hours of reaction.
Based on the study of morphology and composition evolution
of products, we confirmed the course and mechanism of
controlled NCPs synthesis: that the polymerization starts from
Fe3O4-including micelles, proceeds only on the surface of
clusters, and results in controlled growth of the polymer shell
toward uniform NCPs. These findings provide theoretical and
methodological fundamentals for the preparation of high
quality NCPs.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.9b01103.
DLS results of colloidal Fe3O4 clusters (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*Phone: (+86)010-62773017. E-mail: luyc@tsinghua.edu.cn.
ORCID
Xiaojing Liu: 0000-0002-5264-1462
Yangcheng Lu: 0000-0003-0935-9186
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors were granted financial support from the National
Natural Science Foundation of China [grant numbers
21422603 and U1662120].
■
REFERENCES
(1) Van Herk, A. M. Historical overview of (mini)emulsion
polymerizations and preparation of hybrid latex particles. Adv.
Polym. Sci. 2010, 233, 1.
(2) Li, S.; Lin, M. M.; Toprak, M. S.; Kim, D. K.; Muhammed, M.
Nanocomposites of polymer and inorganic nanoparticles for optical
and magnetic applications. Nano Rev. 2010, 1, 5214.
(3) Lin, Y.; Wang, S. X.; Zhang, Y. J.; Gao, J. G.; Hong, L.; Wang, X.;
Wu, W.; Jiang, X. Q. Ultra-high relaxivity iron oxide nanoparticles
confined in polymer nanospheres for tumor MR imaging. J. Mater.
Chem. B 2015, 3, 5702.
(4) Chen, P. F.; Song, H.; Yao, S.; Tu, X. Y.; Su, M.; Zhou, L.
Magnetic targeted nanoparticles based on β-cyclodextrin and chitosan
8146
Article
for hydrophobic drug delivery and a study of their mechanism. RSC
Adv. 2017, 7, 29025.
(5) Ghazanfari, M. R.; Kashefi, M.; Shams, S. F.; Jaafari, M. R.
Perspective of Fe3O4 Nanoparticles Role in Biomedical Applications.
Biochem. Res. Int. 2016, 2016, 7840161.
(6) Sun, Y.; Zheng, Y. Y.; Li, P.; Wang, D.; Niu, C. C.; Gong, Y. P.;
Huang, R. Z.; Wang, Z. B.; Wang, Z. G.; Ran, H. T. Evaluation of
superparamagnetic iron oxide-polymer composite microcapsules for
magnetic resonance-guided high-intensity focused ultrasound cancer
surgery. BMC Cancer 2014, 14, 800.
(7) Stevens, P. D.; Fan, J. D.; Gardimalla, H. M. R.; Yen, M.; Gao, Y.
Superparamagnetic nanoparticle-supported catalysis of suzuki cross-
coupling reactions. Org. Lett. 2005, 7, 2085.
(8) Kainz, Q. M.; Reiser, O. Polymer- and dendrimer-coated
magnetic nanoparticles as versatile supports for catalysts, scavengers,
and reagents. Acc. Chem. Res. 2014, 47, 667.
(9) Gao, R. X.; Cui, X. H.; Hao, Y.; Zhang, L. L.; Liu, D. C.; Tang, Y.
H. A highly-efficient imprinted magnetic nanoparticle for selective
separation and detection of 17 -estradiol in milk. Food Chem. 2016,
194, 1040.
(10) Ge, F.; Li, M. M.; Ye, H.; Zhao, B. X. Effective removal of heavy
metal ions Cd2+, Zn2+, Pb2+, Cu2+ from aqueous solution by polymer-
modified magnetic nanoparticles. J. Hazard. Mater. 2012, 211−212,
366.
(11) Montagne, F.; Mondain-Monval, O.; Pichot, C.; Elaïssari, A.
Highly magnetic latexes from submicrometer oil in water ferrofluid
emulsions. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 2642.
(12) Kloust, H.; Poselt, E.; Kappen, S.; Schmidtke, C.; Kornowski,
A.; Pauer, W.; Moritz, H. U.; Weller, H. Ultrasmall biocompatible
nanocomposites: a new approach using seeded emulsion polymer-
ization for the encapsulation of nanocrystals. Langmuir 2012, 28,
7276.
(13) Paulis, M.; Asua, J. M. Knowledge-based production of
waterborne hybrid polymer materials. Macromol. React. Eng. 2016,
10, 8.
(14) Capek, I. Sterically and electrosterically stabilized emulsion
polymerization. Kinetics and preparation. Adv. Colloid Interface Sci.
2002, 99, 77.
(15) Horák, D.; Chekina, N. Preparation of magnetic poly(glycidyl
methacrylate) microspheres by emulsion polymerization in the
presence of sterically stabilized iron oxide nanoparticles. J. Appl.
Polym. Sci. 2006, 102, 4348.
(16) Aslan, K.; Perez-Luna, V. H. Surface modification of colloidal
gold by chemisorption of alkanethiols in the presence of a nonionic
surfactant. Langmuir 2002, 18, 6059.
(17) Li, X.; Lenhart, J. J. Aggregation and dissolution of silver
nanoparticles in natural surface water. Environ. Sci. Technol. 2012, 46,
5378.
(18) Naqvi, S.; Samim, M.; Abdin, M. Z.; Ahmed, F. J.; Maitra, A.
N.; Prashant, C. K.; Dinda, A. K. Concentration-dependent toxicity of
iron oxide nanoparticles mediated by increased oxidative stress. Int. J.
Nanomed. 2010, 2010, 983.
(19) Kingshott, P.; Griesser, H. J. Surfaces that resist bioadhesion.
Curr. Opin. Solid State Mater. Sci. 1999, 4, 403.
(20) Gulyaev, A. E.; Gelperina, S. E.; Skidan, I. N.; Antropov, A. S.;
Kivman, G. Y.; Kreuter, J. Significant transport of doxorubicin into the
brain with polysorbate 80-coated nanoparticles. Pharm. Res. 1999, 16,
1564.
(21) Wilson, B.; Samanta, M. K.; Santhi, K.; Kumar, K. P. S.;
Paramakrishnan, N.; Suresh, B. Targeted delivery of tacrine into the
brain with polysorbate 80-coated poly(n-butylcyanoacrylate) nano-
particles. Eur. J. Pharm. Biopharm. 2008, 70, 75.
(22) Sun, W. Q.; Xie, C. S.; Wang, H. F.; Hu, Y. Specific role of
polysorbate 80 coating on the targeting of nanoparticles to the brain.
Biomaterials 2004, 25, 3065.
(23) Ozdeger, E.; Sudol, E. D.; El-Aasser, M. S.; Klein, A. Role of the
nonionic surfactant triton X-405 in emulsion polymerization. III.
Copolymerization of styrene and n-butyl acrylate. J. Polym. Sci., Part
A: Polym. Chem. 1997, 35, 3837.
DOI: 10.1021/acs.iecr.9b01103
Ind. Eng. Chem. Res. 2019, 58, 8140−8147
Industrial & Engineering Chemistry Research Article

(24) Zhang, Y. W.; Zhuang, X.; Gu, W. J.; Zhao, J. X. Synthesis of

polyacrylonitrile nanoparticles at high monomer concentrations by
AIBN-initiated semi-continuous emulsion polymerization method.
Eur. Polym. J. 2015, 67, 57.
(25) Liu, B. J.; Wang, Y. J.; Zhang, M. Y.; Zhang, H. X. Initiator
systems effect on particle coagulation and particle size distribution in
one-step emulsion polymerization of styrene. Polymers 2016, 8, 55.
(26) Wu, C. C.; Kong, X. M.; Yang, H. L. Controllable preparation
of high-yield magnetic polymer latex. J. Colloid Interface Sci. 2011,
361, 49.
(27) Perro, A.; Duguet, E.; Lambert, O.; Taveau, J. C.; Bourgeat-
Lami, E.; Ravaine, S. A chemical synthetic route towards “colloidal
molecules. Angew. Chem., Int. Ed. 2009, 48, 361.
(28) Xu, X. L.; Friedman, G.; Humfeld, K. D.; Majetich, S. A.; Asher,
S. A. Synthesis and utilization of monodisperse superparamagnetic
colloidal particles for magnetically controllable photonic crystals.
Chem. Mater. 2002, 14, 1249.
(29) Cui, L. L.; Xu, H.; He, P.; Sumitomo, K.; Yamaguchi, Y.; Gu, H.
C. Developing a hybrid emulsion polymerization system to synthesize
Fe3O4/polystyrene latexes with narrow size distribution and high
magnetite content. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 5285.
(30) Mosafer, J.; Abnous, K.; Tafaghodi, M.; Jafarzadeh, H.;
Ramezani, M. Preparation and characterization of uniform-sized
PLGA nanospheres encapsulated with oleic acid-coated magnetic-
Fe3O4 nanoparticles for simultaneous diagnostic and therapeutic
applications. Colloids Surf., A 2017, 514, 146.
(31) Jain, T. K.; Morales, M. A.; Sahoo, S. K.; Leslie-Pelecky, D. L.;
Labhasetwar, V. Iron oxide nanoparticles for sustained delivery of
anticancer agents. Mol. Pharmaceutics 2005, 2, 194.
(32) Schmidtke, C.; Eggers, R.; Zierold, R.; Feld, A.; Kloust, H.;
Wolter, C.; Ostermann, J.; Merkl, J. P.; Schotten, T.; Nielsch, K.;
Weller, H. Polymer-assisted self-assembly of superparamagnetic iron
oxide nanoparticles into well-defined clusters: controlling the
collective magnetic properties. Langmuir 2014, 30, 11190.
(33) Di Corato, R.; Piacenza, P.; Musaro, M.; Buonsanti, R.; Cozzoli,
P. D.; Zambianchi, M.; Barbarella, G.; Cingolani, R.; Manna, L.;
Pellegrino, T. Magnetic-fluorescent colloidal nanobeads: preparation
and exploitation in cell separation experiments. Macromol. Biosci.
2009, 9, 952.
(34) Weiss, J.; McClements, D. J. Mass transport phenomena in oil-
in-water emulsions containing surfactant micelles: Solubilization.
Langmuir 2000, 16, 5879.
(35) Okubo, M.; Kobayashi, H.; Matoba, T.; Oshima, Y.
Incorporation of nonionic emulsifiers inside particles in emulsion
polymerization: Mechanism and methods of suppression. Langmuir
2006, 22, 8727.
(36) Elvira, K. S.; Casadevall i Solvas, X.; Wootton, R. C. R.; De
Mello, A. J. The past, present and potential for microfluidic reactor
technology in chemical synthesis. Nat. Chem. 2013, 5, 905.
(37) Jahn, A.; Vreeland, W. N.; Gaitan, M.; Locascio, L. E.
Controlled vesicle self-assembly in microfluidic channels with
hydrodynamic focusing. J. Am. Chem. Soc. 2004, 126, 2674.

8147 DOI: 10.1021/acs.iecr.9b01103

Ind. Eng. Chem. Res. 2019, 58, 8140−8147