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Backbone-Degradable Acrylate Latex: Toward Overcoming

Hydrolysis Limitations of Cyclic Ketene Acetal Monomers
Srinivasa Reddy Mothe,# Wenguang Zhao,# Alexander M. van Herk, and Praveen Thoniyot*
Cite This: https://doi.org/10.1021/acs.macromol.3c02474 Read Online

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ABSTRACT: Latex particles made with radical emulsion polymer-

ization contain all carbon-backbone polymer chains, which are
nonhydrolyzable and nonbiodegradable in the environment and
hence pose a huge challenge as persistent pollutants. Radical ring-
opening copolymerization (rROP) of cyclic ketene acetals (CKAs)
such as 2-methylene-1,3-dioxepane (MDO) with vinyl monomers
is an interesting approach being explored intensely for introducing
degradable ester groups in the polymer backbones, opening up the
potential of synthesizing biodegradable copolymers. However,
carrying out such reactions in an aqueous medium to obtain
biodegradable dispersions is very challenging due to the hydrolytic
instability of CKAs. There are conflicting reports on preparing degradable lattices via rROP of MDO with vinyl acetate (VAc)
monomers, but subsequent detailed reaction parameters were published, which show that under the right conditions, successful
copolymerizations can be performed. We report that the use of neutral surfactants, high pH, and stabilizing comonomers play a
crucial role in the successful incorporation of degradability in the polymer backbone during emulsion copolymerization. This is the
first report on the synthesis of acrylate copolymers with the incorporation of hydrolytic degradability (utilizing MDO) under
potentially more industrially feasible emulsion polymerization conditions. The findings underscore the potential for further
improvement in this area. The results in the current study provide further insight into the breadth of parameters that must be
carefully considered to produce biodegradable lattices via the rROP of CKAs.

■ INTRODUCTION
A wide variety of acrylate-based polymers have been developed
over the years with applications such as plastics, waterborne
coatings,1 adhesives,2 nanocomposites,3 drug carriers,4,5 and
scale control agents.6 Acrylate copolymers are commonly used
in personal or consumer care applications due to their tunable
functionalities that enable the incorporation of required
benefits in formulations. At the same time, it is almost
unavoidable that these polymers wind up in the environment.
With introducing degradable units in the carbon−carbon main
chain of these polymers, the accumulation of solid waste in the
environment,7 particularly the leakage of synthetic polymers
from several consumer care and agricultural industries to our
oceans, might be alleviated. There has been a rapidly increasing
interest in this area in recent years.8−10 The degradable version
of acrylate copolymers is typically prepared by free-radical ring-
opening polymerization (rROP) of cyclic ketene acetal (CKA)
with vinyl acrylate monomers. The early work of CKA
polymerization by Bailey and co-workers in the 1980s unveiled
the synthesis of degradable copolymers by introducing
cleavable ester linkages into the backbone of traditional
nondegradable polymers, which led to advanced applications
of these degradable plastics.11−17 It is noteworthy that the
degradability of these copolymers is often demonstrated under
alkaline conditions. However, it is crucial to note that this
alone does not imply biodegradability; the latter is contingent
on the biodegradability of the formed oligomers.18
Later on, rROP of CKAs and vinyl monomers is routinely
exploited18−22 and has been employed to prepare degradable
poly(styrene), 23 poly(methacrylate),24−26 various poly-
(acrylates),27−29 poly(vinyl ethers),30 and poly(vinyl ace-
tates).31 The degradable polymers synthesized via the
incorporation of CKA units usually require high temperatures
and water-free conditions.32 These polymerizations are neither
suitable in combination with certain functional groups nor can
they be easily performed in water.33,34 Polymer dispersions of
degradable acrylates made by emulsion polymerization are of
great interest due to the use of water as a nontoxic and green
reaction medium. Of course, the challenge is the hydrolysis of
CKAs due to the diffusion of the monomer from the droplets
to the aqueous phase into the particles. Miniemulsion
polymerization does not require the transport of monomer
Received: November 30, 2023
Revised: February 12, 2024
Accepted: February 22, 2024

© XXXX American Chemical Society https://doi.org/10.1021/acs.macromol.3c02474

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Scheme 1. Emulsion Polymerization of MDO and MMA and HEA to Afford Main-Chain-Degradable Poly(methyl
methacrylate) Nanoparticles
through the aqueous phase, in contrast to regular emulsion
polymerization (see later for a further discussion).35
Miniemulsion polymerization has led to a wide variety of
surface functionalities and the encapsulation of different kinds
of materials, e.g., drugs, dyes, inorganic materials, etc. In 2012,
the Landfester group published a miniemulsion process for
making degradable polymeric nanoparticles via rROP of 5,6-
benzo-2-methylene-1,3-dioxepane (BMDO) with methyl
methacrylate (MMA) and styrene; this was the first report in
which water is the continuous phase.36 It must be remarked
here that both the reactivity ratios and the hydrolytic stability
of BMDO are more favorable than that of MDO. Although
miniemulsion polymerization has been explored for the
development of a wide range of polymer materials,37 its
scope is typically on very hydrophobic monomers. Currently
commercial products derived from miniemulsion polymer-
ization are much less prevalent compared to emulsion
polymerization products.38 After this miniemulsion work,
almost a decade passed without significant progress in aqueous
polymerization attempts in CKA chemistry, even though
success was reported in creating degradable latex with other
chemistries that insert degradability, such as the example of
dibenzo[c,e]oxepane-5-thione (DOT) copolymerization with
acrylates and styrene.39 There is still a need for the CKA-based
breakable bond insertion since ester groups might be preferred
over the thioester groups, where oligomer yellowing and smell
associated with thiol groups can be an issue in various
applications, which will not be the case for carboxyl esters
derived from CKA monomers.
A breakthrough in the aqueous phase polymerization of
CKAs was recently reported by Carter et al. where a high
incorporation of 2-methylene-1,3-dioxepane (MDO) was
achieved by emulsion copolymerization of MDO with vinyl
acetate (VAc) as the comonomer and the resulting latex was
utilized for biodegradable single-use paper coatings.40 The
authors mentioned a favorable reactivity ratio, adequate pH
adjustment, and high instantaneous conversions (starved-feed
addition of monomers) as the main reason for the high
incorporation of MDO in the vinyl latex. The starved
monomer feeding strategy resulted in a very short residence
time of MDO in its monomeric form in water, minimizing the
hydrolysis. However, subsequent work by Agarwal et al. failed
to reproduce the high incorporation of degradability in VAc
latex, indicating that reproducibility is still challenging.41 Their
kinetic hydrolysis studies on MDO in water under a variety of
pH and polarity conditions with cosolvents have concluded
that preparing biodegradable emulsion polymers using the
rROP of MDO and vinyl monomers (including VAc) is still a
challenge. Following these conflicting reports, Carter et al.
provided more in-depth data and quantitative analysis tools in
a recent report, giving further proof for the successful emulsion
polymerization of VAc and MDO.42 The main differences
between the work of Carter and that of Agarwal are that pH
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Article
control was not as strict in the latter case and the instantaneous
monomer conversions were not as close to starved conditions
(this is most likely due to a different way of administering the
redox initiation system).42 Despite the successful emulsion
copolymerization of MDO and VAc, there are no reports on
the emulsion copolymerization of MDO and acrylates. The
main reason is the very unfavorable reactivity ratios of the two
monomers (rMDO = 0.04, rMMA = 3.5)20 coupled with the
strong hydrolytic instability. With BMDO, there are more
favorable reactivity ratios with most monomers, for example,
BMDO and MMA (rBMDO = 0.53 and rMMA = 1.96) and a
higher hydrolytic stability, for this combination in emulsion
copolymerization, about 6% insertion of ester bonds was
achieved and degradability was reported.43 Recently, we
further explored the MDO hydrolysis mechanism in water
and evaluated conditions that enabled aqueous phase solution
copolymerization of MDO with hydroxyethyl acrylate and
acrylamide.44 In both cases, we could only observe very
minimal incorporation of MDO in the copolymer (as
evidenced by the hydrolysis experiments of the resulting
copolymer), and the majority of MDO underwent hydrolysis.
However, this study provided the hope that under the right
conditions, MDO emulsion copolymerization could be carried
out even with methacrylates, as predicted by Bailey who
pioneered the field decades ago.45 From this study, it became
clear that the hydrolysis of MDO is predominantly acid-
catalyzed.44 In the case of VAc-MDO, the pH was limited by
the occurrence of saponification of VAc and was optimized to
pH = 8. Even though VAc and MDO have favorable reactivity
ratios, we chose to work with acrylates, as acrylates do not
undergo saponification like VAc. Therefore, acrylates have less
limitations to high pH conditions, which suitably slow down
the hydrolysis of CKA monomers.44,45 Following this
approach, we report the synthesis of degradable poly(MMA)
nanoparticles via the batch emulsion copolymerization of
MMA with MDO and 2-hydroxyethyl acrylate (HEA) with a
75:20:5 ratio, respectively. Polymers with up to 9 mol % of
degradable units in the main-chain polymer backbone were
obtained. Subsequent hydrolytic degradation of the polymer
results in small oligomeric degradation products (Scheme 1).
We realize that the batch approach is not optimal for monomer
pairs with significantly different reactivity ratios. Further
optimization is deemed feasible, and a semibatch approach is
considered with a more optimal monomer addition profile for
these types of monomers.29 This strategy will be investigated in
our future studies to enhance the synthesis process, including
aspects such as a higher solid content, yield, and achieving
better control over reactivity, particularly regarding MDO
incorporation in the polymer backbone. Even though the
competing hydrolysis could not be avoided fully under our
current reaction conditions, we expect this study to provide a
framework of conditions under which degradable acrylate latex
can be successfully prepared by rROP of CKA monomers.
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■ EXPERIMENTAL SECTION
Materials. All chemicals were purchased from Sigma-Aldrich and
Table 1. Optimization of Reaction Conditions for the
Synthesis and Characterization of Poly(MDO-co-MMA)
used as received unless stated otherwise. MDO12 and PEG-b-PCL46 Nanoparticles through Emulsion Polymerization to Obtain
were synthesized as previously reported. Monomers: ethylene glycol Stable Dispersions (EM3, EM5−EM7, and EM9) and with
dimethacrylate (EGDMA), MMA, HEA, and 2-hydroxyethyl meth- Improved MDO% Incorporation (EM4)a
acrylate (HEMA), n-butyl acrylate (BA), ethyl acrylate (EA), 2-
(dimethylamino)ethyl methacrylate (DMAEMA), methyl acrylate initial comonomer MDO
(MA), n-butyl methacrylate (BMA), 2-ethylhexyl acrylate (EHA), and mixture of incorporation in
MMA:MDO:HEA the final polymer
allyl methyl acrylate (AMA) were purchased from Sigma-Aldrich and experiment (mol %) conditions (mol %)b
passed through basic Al2O3 to remove inhibitors before polymer- c
EM1 80:20:0 SDS (0.125 g),
ization. Initiators: ammonium persulfate (APS) and 2,2′-azobis(2- TBAB (0.2 g) c
methylpropionamidine) dihydrochloride (V-50) were purchased from EM2 75:20:5
Sigma-Aldrich and recrystallized from methanol before use. EM3 75:20:5 triton X-100 3 ± 0.07
(0.125 g),
Surfactants: Triton X-100, sodium dodecyl sulfate (SDS), Poloxamer, TBAB (0.2 g)
Ryoto sugar ester, Span 80, Span 85, Triton X-405, Tween 20, Tween
EM4 75:20:5 triton X-100 9 ± 0.07
80, dihexyl sulfosuccinate sodium, sodium dodecylbenzene sulfonate (0.125 g)
EM5d 75:20:5 7 ± 0.07
(SDBS), cetyltrimethylammonium bromide (CTAB), and benzetho-
nium chloride (hyamine) were purchased from Sigma-Aldrich and EM6e 75:20:5 7 ± 0.02
used as received. Sodium hydroxide (NaOH), potassium hydroxide EM7 75:20:5 poloxamer-188 6 ± 0.02
(KOH), and tetra-n-butylammonium bromide (TBAB) were (0.125 g)
purchased from Sigma-Aldrich and used as received. 5 M NaOH EM8 80:20:0 triton X-100 <1
(0.125 g)
was prepared and stored as a stock solution. Chloroform-d (CDCl3)
was purchased from Cambridge Isotope Laboratories (CIL) and used EM9f 75:20:5 PEG-b-PCL 6
(0.125 g)
as received. The solvents tetrahydrofuran (THF; contains 0.005% of a
water), methanol (MeOH; contains 0.01% of water), and chloroform All polymerizations were conducted using APS initiator (0.3 g),
(CHCl3) were purchased from VWR and used as received. water (12 g), and aq. NaOH (8 g), maintaining a pH > 10 at 70 °C
Chloroform-d (CDCl3) was passed through anhydrous Na2CO3 to for 4 h. bDetermined by 1H NMR analysis, comparing the protons
remove any traces of internally formed hydrochloric acid, which may from the ring-opening of MDO with those from the methyl ester of
cause hydrolysis of polyester and unreacted MDO, ensuring a more MMA. cObserved only poly(MMA) and MDO hydrolyzed product.
d
straightforward analysis process. Repeat of EM4 to check the reproducibility. eUsed HEMA in place
Methods. Preparation of Poly(MDO-co-MMA) (EM1 and EM8) of HEA. fObserved low solid content (∼2 wt %) due to a significant
and Poly(MDO-co-MMA-co-HEA) (EM2) Nanoparticles. In a 50 mL amount of particle aggregation during the reaction.
single-neck round-bottom flask, a stirred solution of SDS (0.125 g; for
EM1 and EM2) and TBAB (0.2 g; for EM1 and EM2) or Triton X- prepared, added to the reaction mixture in one portion, and purged
100 (0.125 g; for EM8) in deionized (DI) water (12.0 g) was with argon gas for another 1 min. The resulting emulsion was
prepared (refer to Table 1). 5 M NaOH (5 M, 4.0 g) was then added monitored to maintain a pH > 10 throughout the reaction by adding
dropwise under argon gas for 2 min. The solution was purged with an additional 5 M NaOH dropwise. It was observed that the reaction
argon gas for 30 min at 70 °C with a stirring speed of 705 rpm. APS pH dropped rapidly, necessitating the periodic addition of 5 M NaOH
(0.3 g) was dissolved in 0.4 mL of DI water, and then argon gas was to maintain the desired pH. Approximately, a total of 8.0 g of 5 M
dropwise added to the reaction mixture and purging was continued NaOH, including the initial 4.0 g feed, was consumed throughout the
for an additional 5 min. A monomer mixture (4 g of MMA, 1 g of reaction. The reaction was stirred at 70 °C for 4 h. After this time,
MDO for EM1 and EM8 or 3.75 g of MMA, 1 g of MDO and 0.25 g sampling was done to estimate the reaction conversion using 1H
of HEA for EM2) was prepared and introduced to the reaction NMR analysis. Later, the reaction was quenched by rapid cooling and
mixture in one portion, followed by an argon gas purging for another purified with DI water through three consecutive centrifugations at
min. The resulting emulsion was monitored to maintain a pH > 10 7830 rpm for 45 min each, removing any residual monomers,
throughout the reaction by the periodic dropwise addition of 5 M hydrolyzed MDO, NaOH, and surfactant. In each purification step,
NaOH. Approximately 8.0 g of 5 M NaOH, including the initial 4.0 g the sedimented solid particles were separated from supernatants by
feed, was consumed during the reaction. The reaction proceeded at 70 decantation. The supernatant contained residual monomers, hydro-
°C for 4 h, after which sampling was performed to estimate the lyzed MDO, NaOH, and surfactant. Following purification, the
reaction conversion by 1H NMR analysis. The reaction was quenched resulting white solid nanoparticles were dried in a vacuum oven at 40
by rapid cooling and purified with DI water through three consecutive °C for 16 h and were analyzed for MDO incorporation with 1H NMR
centrifugations at 7830 rpm for 45 min each, removing any residual analysis. The solid content was 5 wt % for EM3−EM7 and 2% for
monomers, hydrolyzed MDO, NaOH, and surfactant. In each EM9.
purification step, the sedimented solid particles were separated from Preparation of Poly(MDO-co-MMA-co-HEA) Nanoparticles
supernatants by decantation. The supernatant contained residual (EM10−EM15) with Various Nonionic Surfactants. The following
monomers, hydrolyzed MDO, NaOH, and surfactant. Following surfactants were utilized in the synthesis of EM10−EM15 nano-
purification, the resulting white solid nanoparticles, obtained after particles (refer to Table 4): Ryoto sugar ester for EM10, Span 80 for
drying in a vacuum oven at 40 °C for 16 h, were analyzed for MDO EM11, Triton X-405 for EM12, Span 85 for EM13, Tween 80 for
incorporation with 1H NMR analysis. EM14, and Tween 20 for EM15. The experimental procedure
Preparation of Poly(MDO-co-MMA-co-HEA) Nanoparticles employed for EM3−EM7 and EM9 was consistent, and the same was
(EM3−EM7 and EM9). To a stirred solution of Triton X-100 applied to these formulations as well. For EM12 and EM13, no
(0.125 g; for EM3−EM6) or Poloxamer-188 (0.125 g; for EM7 only) detectable MDO incorporation was observed by the 1H NMR
or PEG-b-PCL (0.125 g; for EM9 only) and TBAB (0.2 g; for EM3 analysis. The solid content was 5 wt % for EM10 and EM11 and 4%
only) in DI water (12.0 g) in a 50 mL single-neck round-bottom flask for EM14 and EM15.
was added 5 M NaOH (4.0 g) dropwise under argon gas for 2 min Representative Accelerated Hydrolytic Degradation of Poly-
(refer to Table 1). The resulting solution was purged with an argon (MDO-co-MMA-co-HEA) (EM5). To a stirred solution of poly(MDO-
gas for 30 min at 70 °C with 705 rpm. APS (0.3 g) dissolved in 0.4 co-MMA-co-HEA) EM5 (200 mg) in THF (12 mL) was added a
mL of DI water was then added dropwise to the reaction mixture and solution of KOH (400 mg) in MeOH (4 mL) at room temperature.
purged with argon gas for another 5 min. Then, the monomer mixture The reaction mixture was stirred at room temperature for 72 h. The
(3.75 g of MMA, 1 g of MDO and 0.25 g of HEA or HEMA) was reaction mixture was acidified to pH 4−5 with 6 N HCl at 0 °C.

C https://doi.org/10.1021/acs.macromol.3c02474
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Figure 1. 1H NMR (CDCl3) analysis for (a) EM3 (after purification) and (b) EM2 (after purification).
Solvents were evaporated under reduced pressure, and the obtained
solids were dried under a high vacuum for 2 h to remove solvent
traces. CHCl3 (10 mL) was added to the mixture of solids and stirred
at room temperature for 2 h. Undissolved salts were removed by
syringe filtration, and CHCl3 was removed under reduced pressure to
yield a pale yellow viscous degraded polymer mixture (200 mg,
crude).
■ RESULTS AND DISCUSSION
The copolymerization of (meth)acrylates and cyclic ketene
acetals offers a fascinating route for free-radical ring-opening
copolymerization. This process creates interesting degradable
polymers by incorporating degradable units into the acrylate
backbone in a single step.
We attempted emulsion copolymerizations of MMA and
MDO with varying stabilizers at a pH > 10, and the obtained
results are summarized in Table 1. In emulsion polymerization
in water, with MMA/MDO (molar fraction of 80:20 mol %) or
MMA/MDO/HEA (molar fraction of 75:20:5 mol %), APS as
a radical initiator, TBAB as a stabilizer, and SDS as an anionic
surfactant resulted in the exclusive production of poly(MMA)
with over 99% conversion of MMA monomer (EM1 and
EM2) (refer to Figure 1b for representative 1H NMR analysis
of EM2). The MDO (4 g for EM1 and 3.75 g for EM2) was
found to undergo complete hydrolysis during the reaction.
When replacing SDS with Triton X-100, a neutral surfactant,
while retaining other conditions, poly(MDO-co-MMA-co-
HEA) was obtained with 97 mol % of MMA and 3 mol %
of MDO incorporation in the polymer backbone (EM3). This
was achieved from an initial comonomer mixture with a molar
D https://doi.org/10.1021/acs.macromol.3c02474
Article
fraction of 75 mol % of MMA and 20 mol % of MDO. The
remaining MDO from the initial comonomer mixture under-
went hydrolysis. 1H NMR analysis is shown in Figure 1 for
comparison showing EM2 together with EM3 to distinguish
the incorporated poly(MDO) protons in the polymer
backbone. The important factors for success are to obtain a
stable latex, minimize MDO hydrolysis, and incorporate MDO
in the copolymer. Regarding the stability, we observed that
neutral surfactants were improving stability; regarding MDO
hydrolysis, the use of high pH was important as it is well-
known that the hydrolysis of MDO is minimized at high pH
compared to neutral and acidic pH conditions.41,42,44 Of
course, currently in this study, the batch process is used, which
is not optimal for the reactivity ratios at hand, so further
optimization is certainly possible via a semibatch process.29 We
attempted the worst-case scenario with using a batch reaction;
furthermore, semibatch would necessitate the presence of
larger amounts of MDO at the beginning of the reaction,
potentially increasing hydrolysis levels, warranting further
investigation. Based on these current observations, it is
hypothesized that the neutral surfactant Triton X-100 in
combination with the hydrophilic nature of the surface
hydroxyl groups from HEA (or HEMA) at high pH plays a
crucial role in stabilizing the latex particles. At this high pH and
while neutralizing with aqueous NaOH, the ionic strength is
high and ionic stabilization is challenging.41 Another factor
could be the transport of monomer from droplets to latex
particles. Although molecular monomer diffusion is generally
accepted, there is evidence that monomer transport could also
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Table 2. Characterization of Poly(MDO-co-MMA-co-HEA) Nanoparticles (EM3−EM7) and Their Corresponding Oligomeric

Degradation Products by Gel Permeation Chromatography (GPC)
polymer
compositiona polymer before degradation polymer after degradation
conversion of MDO (mol %) in ĐM Mntheo Mn Mw ĐM
experiment MMA/MDO (%)b polymera MMA MDO Mn (Da) Mw (Da) (Mw/Mn) (Da) (Da) (Da) (Mw/Mn)
EM3 99/99 3 0.97 0.03 49,500 283,500 5.72 3300 4600 16,900 3.65
EM4 99/99 9 0.91 0.09 48,500 233,400 4.80 1100 3000 5100 1.67
EM5 99/99 7 0.93 0.07 69,600 312,700 4.48 1400 1000 2700 2.57
EM6 99/99 7 0.93 0.07 46,700 325,900 6.97 1400 2400 3700 1.55
EM7 99/99 6 0.94 0.06 109,900 288,900 2.63 1700 2500 6000 2.34
a
Determined by 1H NMR analysis of the purified sample. bDetermined by 1H NMR analysis of the crude polymeric latex.

occur through direct collisions between monomer droplets and
latex particles. Most evidence is found in miniemulsion
polymerizations,47,48 but there are several papers that also
claim that collisions could be an important monomer transport
mechanism in regular emulsion polymerization (refer to Figure
5).49,50 It was observed that the collision mechanism is favored
when using neutral surfactants (over charged surfactants).50
Although the collision mechanism is useful for completely
water-insoluble species,48 in our case, where avoiding direct
contact between the monomer and water is desirable, the
collision mechanism facilitated by neutral surfactants is likely
to be beneficial.
During the course of optimizing reaction conditions, we
observed a significant improvement in MDO incorporation (9
mol %) when TBAB was not included (EM4). To confirm the
reproducibility of EM4 results, we have repeated the reaction
and found not much difference in polymer composition
(EM5) (for a representative picture of the emulsion polymer
EM5, refer to Figure S26 in the Supporting Information, SI).
Subsequent attempts to modify the reaction conditions by
switching from HEA to HEMA or changing the surfactant from
Triton X-100 to Poloxamer-188 or PEG-b-PCL (EM6, EM7,
and EM9, respectively) did not result in significant alterations
in polymer compositions, except for a lower solid content
observed in the case of PEG-b-PCL. This lower solid content
was likely caused by extensive particle aggregation during the
reaction. To further investigate the impact of HEA, we
conducted a control experiment (EM8), which revealed that in
the absence of HEA, less than 1% of MDO incorporation was
detected along with the formation of some particle aggregates.
For EM3−EM9 lattices, in addition to MDO incorporation
(3−9 mol % out of the initial 20 mol % MDO monomer in the
recipe), the remaining MDO underwent hydrolysis.
At this juncture, it is important to highlight the significant
role of the hydroxyl groups from HEA in maintaining colloidal
stability without imparting charge to the particles. We posit
that maintaining a low particle charge, especially at this
elevated ionic strength and pH, enhances the transport of
monomers through collisions and reduces the chances of
MDO hydrolysis. There are alternative stabilizing hydrophilic
acid monomers, such as acrylic acid (AA) or methacrylic acid
(MAA), which could potentially sustain colloidal stability.51
However, owing to the high reactivity of acid groups with
MDO and the potential hindrance to MDO incorporation in
the polymer backbone, we have not employed them in the
current study.33,34
After polymerization, all polymeric dispersions were purified
with DI water three times by centrifugation at 7830 rpm for 45
min each at room temperature. This process removed residual
E https://doi.org/10.1021/acs.macromol.3c02474
monomers, hydrolyzed MDO, NaOH, and surfactant, ensuring
the purity of the samples before NMR analysis (refer to the
Experimental Section for the detailed procedure). From 1H
NMR of poly(MDO-co-MMA-co-HEA) EM3 or EM5, shown
in Figures 1a and 3b, respectively, peak e at 3.97 ppm and
peaks d between 2.7 and 2.2 ppm are corresponding to
methylene protons (−CH2−C(O)O−CH2−) and −C(O)O−
CH2−, respectively, of the degradable units of polyester. The
methylene protons adjacent to carbonyl (−CH2−C(O)O−)
are often observed as a single peak in the homopolymerization
of MDO22 but it was seen here as two different peaks at 2.7
and 2.2 ppm. The splitting is due to differences in
configuration, and the shift supports a copolymer with a
random distribution.52,53 The higher shifted peak at 2.7 ppm
corresponds to a proton d (Figure 1a) where MDO directly
connected to acrylate and the lower shifted peak at 2.2 ppm
corresponds to the same proton d where MDO monomers
connected within it. Peaks e and/or d are used to estimate the
amount of heterodyads, i.e., the mol % of MDO monomer
coupled to acrylate monomer with the comparison of proton c
(methyl ester of MMA).29 ,52 Peaks 178.2, 177.9, and 177.1
ppm from 13C NMR (Figure 3d) correspond to the carboxylate
of MMA, MDO, and HEA, respectively, and which are also
used to estimate the amount of heterodyads. For 1H NMR
analysis of EM6 and EM7, refer to Figures S1 and S3 in the SI.
It is important to highlight the purity comparison between
EM3 and EM5 through 1H NMR characterization (Figures 1a
and 3b). In EM3, two additional peaks appear around peaks e
+ k, whereas they are absent in EM5. It should be noted that
EM3 was synthesized during the optimization of reaction
conditions, involving the use of the stabilizer TBAB.
Consequently, EM3 may not be as pure as EM5, despite
applying the same purification procedure to eliminate residual
monomers, surfactants, stabilizers, and NaOH in both. We
hypothesize that these two peaks around e + k could be
attributed to the presence of small (polymer) molecules
resulting from the polymerization. The peak area under e + k
and d in EM3 is consistent with that of EM5 (refer to the peak
integration in Figures 1a and 3b).
An approximate error value for MDO incorporation in the
polymer backbone (expressed as a percentage of MDO
incorporation values) was calculated from the signal-to-noise
ratio (SNR) of the methylene protons (−CH2−C(O)O−
CH2−) of MDO (refer to Tables 1, 4, 6, and 7 in the
manuscript and Table S1 in the SI).29
To demonstrate the degradability of poly(MDO-co-MMA-
co-HEA), EM3−EM7 copolymers were subjected to accel-
erated hydrolytic degradation by treating with an excess of
KOH in a 1:3 mixture of MeOH and THF solvent
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combination at room temperature for 72 h, producing short-
chain methacrylate-based oligomers (Table 2 and Figures 2
Figure 2. GPC analysis of poly(MDO-co-MMA-co-HEA) nano-
particles (EM3−EM7) before and after accelerated hydrolytic
degradation.
and 3). The copolymers were degraded by the cleavage of ester
bonds in the polymeric backbone, as revealed by a decrease in
molar mass during hydrolysis. Gel permeation chromatography
(GPC) analysis (Table 2 and Figure 2) was performed before
and after hydrolytic degradation of the copolymers (EM3−
EM7). Copolymers with higher molar mass (Mn = 46 700 Da−
109 900 Da) were degraded into their corresponding
oligomers with lower molar mass (Mn = 1000 Da−4600 Da)
based on the percentage of degradable ester units in the
polymer backbone. The theoretical molar masses of the
oligomers (Mn = 1100 Da−3300 Da) were calculated based on
the mol % of ester units present in the polymer backbone from
1
H NMR (3−9 mol %). The observed molar mass of oligomers
from copolymer EM5 closely matched the theoretical molar
mass (Mn = 1000 Da and Mn = 1400 Da, respectively),
indicating a more or less uniform distribution of cleavable
bonds within the copolymer chains and across different chains.
However, for copolymers EM3, EM4, EM6, and EM7, the
observed molar mass was significantly higher than the
theoretical molar mass (Table 2). This inconsistency in the
observed molar mass of oligomers, as observed in the GPC
analysis of copolymers, could be due to a composition drift
during the batch process. Additionally, the strong interactions
of the hydroxyl groups of HEA with the GPC column could
play a role.42,54 Furthermore, the disparity between EM4 and
its repeating experiment EM5 regarding their theoretical and
observed molar mass of oligomers may suggest a batch-to-
batch variation, a common occurrence in emulsion polymer-
ization, especially under manual control at the lab scale. This
variability could arise from minor fluctuations in the
temperature, stirring, and pH control. Polydispersity (Đ)
values were recorded as 2.63−6.97 for purified polymers and
1.55−3.65 for oligomers. A control experiment of non-
degradable poly(MMA) with a known molecular weight
distribution (Mn = 28 100 Da) was also subjected to the
same hydrolytic degradation conditions to confirm its
nondegradability nature. As anticipated, no major change in
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Article
molecular weight distribution was observed before (Mn =
28 100 Da) and after (Mn = 27 500 Da) being subjected to
hydrolytic degradation conditions (refer to Figure S17 in the
SI). This finding was further corroborated by 1H NMR analysis
of poly(MMA) before and after hydrolytic degradation,
revealing that the side chains of methyl esters of poly(MMA)
underwent trans-esterification instead of hydrolysis (refer to
Figure S16 in the SI). This observation, indicating no change
in the molecular weight distribution, was consistent with the
absence of hydrolytic degradation in the backbone and side
chains of methyl esters in poly(MMA). Similarly, trans-
esterification was also evident in the oligomeric degradation
products from EM5 during the hydrolytic degradation process
(refer to peak c in Figure 3a).
Aligned with the anticipated outcomes, our observations
from the Supporting Data, including 1H and 13C NMR (Figure
3) and GPC analyses (Table 2 and Figure 2), reveal
noteworthy changes. Specifically, there is a shift in peak e
from 3.9 (Figure 3b) to 4.8 (Figure 3a) in 1H NMR (zoomed
in 6−4 ppm). Additionally, a subtle shift is noted in the
carbonyl peaks of the carboxylate groups, shifting from 178.2,
177.9, and 177.1 ppm (Figure 3d) to 178.1, 177.8, and 176.9
ppm (Figure 3c) for MMA, MDO, and HEA, respectively.
Moreover, the shift in the peak corresponding to the
methylene protons (−C(O)O−CH2−) of MDO from 64.6
(Figure 3d) to 70.3 ppm (Figure 3c) in 13C NMR provides a
clear indication of the degradation of its polymeric backbone.
However, peaks d in the oligomers (Figure 3a) exhibited slight
shifts, attributable to the presence of the newly formed
neighboring group carboxylic acid. The GPC results provide
further corroboration of hydrolytic degradation (Figure 2).
In the rROP of CKA chemistry, the potential side reaction
involving ring-retaining may impact the degradability of the
resulting copolymer as it does not insert an ester bond in the
polymer backbone.22 The formation of a ring-retained
structure in poly(MDO-co-MMA-co-HEA) occurs through
vinyl addition of the propagating radical at the MDO. This
side product is identifiable by the characteristic peak from the
quaternary carbon of the acetal ring, typically observed around
100 ppm in the 13C NMR spectra of the copolymers.
Remarkably, under our current reaction conditions, this
distinctive peak was conspicuously absent (see Figure 3d).
This absence suggests a potential advantage for the
applicability of our approach for industrial conditions, where
the mitigation of this side reaction contributes to the
robustness of the polymerization process.
Next, we turned our attention to characterizing nano-
particles of poly(MDO-co-MMA-co-HEA) (EM3, EM4, and
EM7) using various instruments, including dynamic light
scattering (DLS), scanning electron microscopy (SEM), and
transmission electron microscope (TEM). The particle sizes,
represented by the Z-average and number mean, along with the
polydispersity index (PDI), are presented in Table 3,
complemented by SEM and TEM images (Figure 4). The
dispersions of EM3, EM4, and EM7 exhibited particle sizes of
237.9, 194.9, and 266.6 nm by Z-average and 218, 146.7, and
183.5 nm by number mean, respectively, showcasing a narrow
size distribution. SEM and TEM analyses confirmed the
spherical shape and smooth surface of all three latex particles in
the dispersions. Moreover, the stability of these nanoparticles
was noteworthy, with EM3, EM4, and EM7 displaying good
long-term colloidal stability for over 6 months, showing no
significant change in particle size distribution and no
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Figure 3. (b, d) 1H and 13C NMR (CDCl3) analyses for EM5. (a, c) 1H and 13C NMR (CDCl3) analyses for oligomeric degradation products
resulted from the hydrolytic degradation of EM5.

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Table 3. Dynamic Light Scattering (DLS) Analysis of
Poly(MDO-co-MDO-co-HEA) Nanoparticles (EM3, EM4,
and EM7)
sample ID Z-average (nm) number mean (nm) PDI
EM3 237.9 ± 1.6 218.0 ± 2.1 0.05 ± 0.1
EM4 194.9 ± 2.0 146.7 ± 5.0 0.17 ± 0.1
EM7 266.6 ± 2.2 183.5 ± 15.5 0.27 ± 0.1
sedimentation of particles (for representative results, refer to
Figure S26 and Table S2 in the SI). In contrast, the polymeric
dispersion EM9 showed instability within days (refer to Figure
S27 in the SI). We also investigated the chemical stability of
poly(MDO-co-MMA-co-HEA) EM6 nanoparticles after 5
months of storage at ambient conditions, observing no change
in chemical composition (refer to Figure S2 in the SI)
compared to the freshly prepared sample (refer to Figure S1 in
the SI), as confirmed by 1H NMR analysis.
To investigate the influence of other neutral surfactants, we
conducted further experiments determining the mol % of
MDO incorporation in the main-chain methacrylate polymer
(Table 4). All polymerization conditions remained consistent
with the conditions of EM4 (MMA/MDO/HEA = 75:20:5),
with the only variation being the surfactant used. Reactions
employing Ryoto sugar ester, Span 80, Tween 80, and Tween
20 provided copolymer nanoparticles with 3−4 mol % of
MDO incorporation (EM10, EM11, EM14, and EM15). In
contrast, the use of Triton X-405 and Span 85 led to the
formation of only a poly(MMA) homopolymer with complete
hydrolysis of MDO (EM12 and EM13). Notably, copolymers
EM10, EM11, EM14, and EM15 exhibited nanoparticle
instability within a day. For 1H NMR analysis of EM10,
EM11, EM14, and EM15, refer to Figures S4−S7 in the SI.
Furthermore, we explored the feasibility of employing other
ionic surfactants (both anionic and cationic) as alternatives to
Triton X-100 under the EM4 reaction conditions. However, to
our surprise, none of these experiments resulted in the
formation of poly(MDO-co-MMA-co-HEA); instead, only
poly(MMA) homopolymer formation was observed, as
confirmed by 1H NMR analysis (EM16−EM18 and EM20,
Figure 4. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) analyses of poly(MDO-co-MDO-co-HEA)
nanoparticles. SEM images for (a) EM3, (b) EM4, and (c) EM7. TEM images for (d) EM4 and (e) EM7. Scale bars: (a−c) 1 μm and (d−e) 2 μm.
H https://doi.org/10.1021/acs.macromol.3c02474
Article
Table 5). Even when we attempted one of the reactions with a
different initiator, V-50, the outcome was still unsuccessful
(EM19, Table 5). In all of these reactions (EM16−EM20),
despite the slower rate of hydrolysis in the alkaline medium
with a pH > 10, MDO was observed to undergo complete
hydrolysis during the reaction, resulting in no incorporation of
MDO in the polymer backbone.41,42,44
Subsequently, our focus shifted toward understanding the
mechanism of MDO incorporation in emulsion polymerization
in water (Figure 5). Successful incorporation of MDO while
utilizing neutral micelles could be the result of a series of
intricate mechanistic aspects governing the processes of
monomer and oligomer transport to the micelles as well as
copolymer growth within the micelles. Based on aqueous
solubility, stability, and concentration considerations, there is
also a possibility of homogeneous nucleation of MMA or HEA
in parallel with micellar nucleation in the system. It is likely
that during homogeneous nucleation, there will be substantial
hydrolysis of MDO. In conventional emulsion polymerization
(Figure 5a), where monomers are present in the aqueous phase
in surfactant-stabilized micelles and droplets, the majority of
MMA and MDO is present in the monomer droplets. It then
gets transported to the micelles, enabling propagation in the
micelle. We anticipate diffusion of MDO through the aqueous
phase to lead to the main hydrolytic loss of MDO due to its
hydrolytic instability. This is because MDO, being less stable,
has to diffuse through the aqueous phase and overcome a high
charge density barrier at the micellar interphase to participate
in a polymerization reaction with nonfavorable reactivity ratios.
The high charge density at the micellar water interphase might
also enhance the stabilization of the polar transition state of
hydrolysis, leading to complete hydrolysis. In our present
reaction conditions (Figure 5b), the neutral micelle interface
does not have a highly polar double layer. Furthermore, as
discussed before, the neutral micelles might allow MDO to be
transported into the micelle through direct collisions with the
monomer droplets without undergoing hydrolysis. The chains
containing HEA stabilize the micelle, further maintaining the
neutral interface. In summary, to get MDO incorporation, it
must overcome the hydrolysis challenge by entering micelles
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Table 4. Screening of Various Neutral Surfactants to Investigate the MDO Incorporation in Poly(MDO-co-MDO-co-HEA)
Nanoparticles (EM10−EM15)
final polymer compositionb
experiment surfactant conversion of MMA/MDO (%)a MDO incorporation (mol %)b MMA MDO
EM10 Ryoto sugar ester 99/99 4± 0.15 0.96 0.04
EM11 Span 80 99/99 3± 0.03 0.97 0.03
EM12 Triton X-405 99/99 n.d. 1.0 0
EM13 Span 85 99/99 n.d. 1.0 0
EM14 Tween 80 99/99 3± 0.03 0.97 0.03
EM15 Tween 20 99/99 4± 0.01 0.96 0.04
a
Determined by 1H NMR analysis of the crude polymeric emulsion. bDetermined by 1H NMR analysis of the purified sample. n.d. = not detected.

Table 5. Screening of Anionic and Cationic Surfactants to Investigate MDO Incorporation in Poly(MMA-co-MDO-co-HEA)
Nanoparticles (EM16−EM20)
final polymer composition
a
experiment initiator surfactant conversion of MMA/MDO (%) MDO incorporation (mol %) MMA MDO
EM16 APS DSS 99/99 n.d. 100 0
EM17 APS SDBS 99/99 n.d. 100 0
EM18 APS CTAB 99/99 n.d. 100 0
EM19 V-50 CTAB 99/99 n.d. 100 0
EM20 APS hyamine 99/99 n.d. 100 0
a
Determined by 1H NMR analysis of the crude polymeric emulsion. DSS, dihexyl sulfosuccinate sodium; SDBS, sodium dodecylbenzene sulfonate;
CTAB, cetyltrimethylammonium bromide; hyamine, benzethonium chloride.

Figure 5. Proposed mechanism of MDO transport via (a) diffusion or (b) collision while utilizing charged or neutral surfactants in emulsion
polymerization.

Table 6. Screening of Emulsion Polymerization Conditions Using Various Acrylate Monomersa

Z-average (d MDO incorporation in the final polymer latex
sample initial monomer feeding composition (mol %) nm) PDI (mol %)b
3BA1MDO 71%BA24%MDO 5%HEA 0.2%EGDMA 300.9 0.25 9 ± -.--c
3EA1MDO 71%EA 24%MDO 5%HEA 0.2%EGDMA 347.5 0.08 9 ± -.--c
3MA1MDO 71%MA 24%MDO 5%HEA 0.2%EGDMA 713.1 0.13 5 ± 0.04
1MMA3BA20MDO 19%MMA 56%BA 20%MDO 5%HEA 0.2%AMA 275.6 0.02 10 ± -.--c
1MMA3BA10MDO 21%MMA 64%BA 10%MDO 5%HEA 0.2%AMA 227.5 0.06 3 ± -.--c
3BA1MDO5DMAEMA 71%BA24%MDO 5%DMAEMA 0.2%EGDMA 273.9 0.09 “42 ± -.--c”
3BMA1MDO 71%BMA 24%MDO 5%HEA 0.2%EGDMA 244.3 0.04 10 ± -.--c
1BA2BMA1MDO 24%BA 47%BMA 24%MDO 5%HEA 0.2% 228.2 0.07 “5 ± -.--c”
EGDMA
3EHA1MDO 71%EHA 24%MDO 5%HEA 0.2%EGDMA aggregate n.d.

a
All polymerizations were conducted using APS initiator (0.3 g), Triton X-100 (0.125 g), water (12 g), and aq. NaOH (pH > 10, 8 g) at 70 °C for
4 h. bDetermined by 1H NMR analysis of the purified sample. BA, n-butyl acrylate; EA, ethyl acrylate; MA, methyl acrylate; DMAEMA, 2-
(dimethylamino)ethyl methacrylate; BMA, n-butyl methacrylate; EHA, 2-ethylhexyl acrylate; AMA, allyl methyl acrylate; and EGDMA, ethyl
methyl acrylate. cError is smaller than 0.01.

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Table 7. GPC Analysis of Copolymer Molar Mass Distribution before and after Hydrolytic Degradation
polymer before degradation polymer after degradation
sample MDO incorporation (mol %) Mn (Da) Mw (Da) Đ (Mw/Mn) Mntheo (Da) Mn (Da) Mw (Da) Đ (Mw/Mn)
3BA1MDO 9 ± 0.00 32,900 105,200 3.12 1400 700 1000 1.36
3EA1MDO 9 ± 0.00 21,100 83,100 3.92 1100 800 950 1.18
3MA1MDO 5 ± 0.04 45,800 108,500 2.36 1700 700 970 1.39
1MMA3BA20MDO 10 ± 0.00 8,300 27,700 3.31 1200 400 580 1.41
1MMA3BA10MDO 3 ± 0.00 14,500 42,000 2.90 4000 600 700 1.11
3BA1MDO5DMAEMA 42 ± 0.00a 26,800 90,200 3.36 300 310 1.10
3BMA1MDO 10 ± 0.00 17,700 73,200 4.13 1400 3400 9000 2.64
1BA2BMA1MDO 5 ± 0.00a 11,380 32,000 2.81 2600 6500 2.47
a
Determination of MDO incorporation was conducted through Mn of oligomeric degradation products by GPC analysis, as it proved challenging
by 1H NMR due to overlapping peaks.

rapidly, where, in the hydrophobic environment, it takes part in
polymerization rather than hydrolysis.55 The neutral micelle
also promotes an alternate mechanism of transport of
monomers through collisions47−49 (Figure 5b).
It is to be noted that the hydrophilic−lipophilic balance
(HLB) or the orientation of hydrophilic and lipophilic groups
in a surfactant plays a crucial role in stabilizing and growing
radical polymer particles in the continuous phase of an
emulsion polymerization system. The HLB value, measured on
an arbitrary scale from 0 to 20, indicates the size and strength
of the polar portion relative to the nonpolar portion of the
nonionic surfactant molecule, where 0 represents complete
lipophilicity and 20 denotes complete hydrophilicity. For oil-
in-water (o/w) emulsions, the surfactant HLB is ideally in the
range of 8−16.56 Within this range, the hydrophilic part of the
surfactant aligns toward the water, while the lipophilic part
aligns toward the oil, effectively stabilizing the o/w emulsion.
Surfactants with HLB values outside this range (8−16) may
not be able to form stable o/w emulsions. Upon scrutinizing
Table 4 and comparing it with Triton X-100, it becomes
apparent that the HLB value of Triton X-100 (∼13.5) is better
suited for o/w emulsions, contributing to improved MDO
incorporation and long-term stable emulsion. In contrast, Span
80 (∼4.3), Triton X-405 (∼16.7), Span 85 (∼1.8), Tween 80
(∼15), and Tween 20 (∼16.7) either fall outside or closely
approach the necessary HLB range. This observation might be
an explanation for the limited or negligible incorporation of
MDO into the polymer backbone for the latter surfactants.
We have conducted further reactions using other acrylate
monomers (BA, EA, MA, MMA/BA, and BMA/BA mixtures),
and the results are summarized in Table 6. All polymerization
conditions remained unchanged from the conditions of EM4
except for switching monomer types and compositions and
performing with cross-linkers (AMA and EGDMA). As
discussed in the Introduction section, poly(VAc) containing
MDO-derived esters in emulsions has already been
reported,40,42 and we did not explore MDO incorporation
under our conditions since the high basicity of the medium
might be complicating the system due to hydrolysis of the
acetate side groups.
When different acrylate monomers are compared, it
becomes evident that more hydrophobic acrylate monomers
tend to achieve higher MDO% incorporation into their
polymer backbone. This trend is noticeable in the comparison
between 3BA1MDO and 3MA1MDO, where the former
exhibits a 9 mol % MDO incorporation, while the latter shows
a 5 mol % MDO incorporation. Similar trends were obtained
in the cases of 3EA1MDO, 1MMA3BA20MDO, and
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3BMA1MDO, with the observed MDO incorporation of 9,
10, and 10 mol %, respectively. However, when the monomer
mixtures become excessively hydrophobic, early aggregation
occurs, accompanied by hardly any incorporation of MDO in
the polymer backbone. This phenomenon is exemplified by
3EHA1MDO. In conclusion, compositions containing linear
and more hydrophobic monomers, such as BA, EA, and BMA,
tend to provide higher percentages of MDO incorporation into
their corresponding polymer backbone. Upon examining
samples 1MMA3BA20MDO and 1MMA3BA10MDO, it was
found that the recipes with a lower level of MDO also showed
a lower amount of MDO incorporation in the final polymer
latex, as revealed by 1H NMR analysis. This suggests that less
MDO is copolymerized, and consequently, a significant
portion of MDO underwent hydrolysis. For samples
3BA1MDO5DMAEMA and 1BA2BMA1MDO, the calculation
of MDO was challenging by 1H NMR as the corresponding
peaks were found to be overlapping. Hence, the level of MDO
incorporation was roughly estimated by the molecular weight
of the oligomeric degradation products (Table 7). For 1H
NMR analysis of samples from Table 6, refer to Figures S8−
S15 in the SI.
Next, we treated the copolymers from Table 6 with an excess
of KOH in a 1:3 mixture of MeOH and THF solvent
combination at room temperature for 72 h, resulting in short-
chain acrylate-based oligomers. GPC analysis (Figure 6 and
Table 7) was performed before and after the hydrolytic
degradation of copolymers. A decrease in molar mass (Mn)
from 8300−45,800 to 300−3400 Da was observed during
hydrolysis as shown in the GPC analysis (Figure 6 and Table
7). It is to be noted that the observed molar masses of the
oligomeric degradation products did not closely match their
theoretical molar masses, possibly due to some interaction of
the resulting carboxyl groups with the GPC column.
Nevertheless, these findings suggest that even in batch
reactions with unfavorable reactivity ratios, some degree of
MDO incorporation remains achievable in emulsion copoly-
merizations, provided specific conditions are met. These
conditions include the presence of neutral surfactants, a
hydroxy-functional comonomer, and a high pH environment.57
For GPC analysis of individual samples from Figure 6, refer to
Figures S18−S25 in the SI.
■ CONCLUSIONS
We report the first batch emulsion copolymerization of MMA
and MDO to obtain degradable latex at high pH and utilize a
neutral surfactant and 5 mol % of hydroxy-functional
costabilizing monomers. NMR spectral analysis and chemical
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Figure 6. GPC analysis of copolymers derived from various vinyl
monomers and their corresponding oligomeric degradation products.
degradation experiments indicate up to 9 mol % of MDO
incorporation in the emulsion polymer backbone. Chemical
degradation studies, followed by GPC analysis, confirm the
incorporation of degradable units via MDO, corroborating the
results of NMR analysis. Use of charged surfactants results in
no incorporation of MDO, leading to its wastage via complete
hydrolysis. Our study indicates that with proper design of the
surfactant system, pH control, and stabilizing monomer
system, emulsion copolymerization can be successful for
acrylate and methacrylate systems. Comparing these new
results with the MDO-VAc system by the Carter group, it is
clear that for MDO-VAc, the favorable reactivity ratios in
combination with starved conditions led to success. In our
work, we combine MDO with other monomers with
unfavorable reactivity ratios, and we do not apply starved
conditions. This makes this work much more challenging and
also more relevant for industrial applications. The essence of
our findings is that in order to minimize hydrolysis under batch
conditions, we need to keep the charge density on the latex
particles as low as possible by utilizing neutral surfactants and a
neutral costabilizing monomer in combination with a high pH.
In the system of Carter, this is not needed. We propose that
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Article
monomer transport by collisions could be favored under these
conditions, whereby we reduce the chance of hydrolysis. This
is all adding to the present know-how in the field of emulsion
copolymerization of CKA and specifically MDO. To the best
of our knowledge, the monomer transport by collisions has not
been invoked before for hydrophilic monomers. The breadth
of parameters considered in this paper can be expanded to the
rROP of CKAs to include monomers with highly unfavorable
reactivity ratios. We are currently exploring industrial-scale
studies on this sustainable latex polymerization process and
developing biodegradable substitutes for free-radical emulsion
polymers.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.macromol.3c02474.
Experimental details; characterization data; 1H NMR
(CDCl3) of poly(MDO-co-MMA-co-HEA); and GPC of
poly(MMA) (a) before and (b) after subjected to
hydrolytic degradation, and representative picture for
the purified poly(MDO-co-MMA-co-HEA) (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Praveen Thoniyot − Institute of Sustainability for Chemicals,
Energy and Environment (ISCE2), Agency for Science,
Technology and Research (A*STAR), Singapore 627833,
Republic of Singapore; Department of Chemical Engineering
and Chemistry, Eindhoven University of Technology, 5600
MB Eindhoven, The Netherlands; orcid.org/0000-0001-
5062-1831; Email: p.thoniyot@tue.nl
Authors
Srinivasa Reddy Mothe − Institute of Sustainability for
Chemicals, Energy and Environment (ISCE2), Agency for
Science, Technology and Research (A*STAR), Singapore
627833, Republic of Singapore; orcid.org/0000-0001-
6415-3311
Wenguang Zhao − Institute of Sustainability for Chemicals,
Energy and Environment (ISCE2), Agency for Science,
Technology and Research (A*STAR), Singapore 627833,
Republic of Singapore
Alexander M. van Herk − Department of the Built
Environment, Building Materials, Eindhoven University of
Technology, 5600 MB Eindhoven, The Netherlands
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.macromol.3c02474
Author Contributions
#
S.R.M. and W.Z. contributed equally to this work. S.R.M.:
experiments, methodology, formal analysis, and data curation.
Z.W.: experiments, methodology, formal analysis, and data
curation. A.M.v.H.: conceptualization, data interpretation,
review, and editing. P.T.: conceptualization, resources,
validation, writing�review and editing, supervision, and
funding acquisition.
Notes
The authors declare the following competing financial
interest(s): A*STAR has filed a patent application
(WO2023075696A3) with Praveen Thoniyot, Srinivasa
Reddy MOTHE, and Wenguang Zhao as inventors for
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Macromolecules pubs.acs.org/Macromolecules
potential future commercialization of the materials produced
by the method.
■ ACKNOWLEDGMENTS
The authors gratefully acknowledge the Agency for Science,
Technology and Research (A*STAR), Science and Engineer-
ing Research Council (SERC), under Specialty Chemicals
AME IAF-PP Programme Grant (Project refs: A1786a0025
and A20G1a0046). The authors extend their gratitude to
Lohitha Rao Chennamaneni for the monomer supply and to
Jean-Baptiste Lena for their assistance in calculating the
approximate error value for MDO incorporation.
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