Progress in Organic Coatings 143 (2020) 105628

Contents lists available at ScienceDirect

Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Preparation, stability and film properties of cationic polyacrylate latex T

particles with various substituents on the nitrogen atom
Chen Huaa, Kaimin Chenb,*, Zun Wanga, Xuhong Guoa,*
a
State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, PR China
b
College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai, 201620, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Cationic latexes have received wide attention due to their special properties and potential applications in wood
Cationic latexes coatings, fabric treatment, etc. However, the practical application of cationic latexes was hindered due to their
Emulsion polymerization poor stability, especially the alkali resistance stability. In this work, various stable cationic polyacrylate latexes
Stability were prepared by an efficient route. Three cationic comonomers, i.e., methacrylatoethyl trimethyl ammonium
Alkali resistance
chloride (DMC), 2-(dimethylamino)ethyl methacrylate (DMAEMA), and 2-aminoethyl methacrylate hydro-
Film properties
chloride (AEMH), were used in the aqueous semi-continuous seeded emulsion polymerization of methyl me-
thacrylate (MMA) and butyl acrylate (BA) using cetyl trimethyl ammonium bromide (CTAB) and 2,2′-azobis[2-
(2-imidazolin-2-yl)propane] dihydrochloride (AIBI) as the cationic emulsifier and initiator, respectively. The
alkali resistance of the latex could be significantly improved by the addition of cationic monomer DMC and be
simply tuned by adjusting DMC dosage. The improved stability of the latex might originate from the higher
charge density on the surface of the latex by the introduction of DMC. Moreover, the effects of initiator dosage,
emulsifier dosage and different cationic comonomers on the latex preparation and the film properties were also
systematically investigated. This work not only introduces an efficient route to prepare cationic latexes with
superior stability, but also paves the way for latexes to be used in applications such as textile finishing, paper
industry, and biomedical field, etc.

1. Introduction at high CTAB or dioctadecyl dimethyl ammonium bromide (DODAB)

concentrations. Polystyrene latexes were obtained and stabilized by
Polymer latexes prepared through emulsion polymerization method CTAC and DTAB, or mixtures of other emulsifiers with the diameter
have been widely used in the fields of coatings [1], paints [2] and fabric between 20 nm and 120 nm [20].
finishing [3]. It is notable that the main research on emulsion poly- However, the latexes using cationic emulsifiers are positively
merization now focused on anionic emulsion polymerization using charged on the surface of the particles and the polymers are charged at
anionic emulsifiers like sodium dodecyl sulfate (SDS) [4–7]. The re- a low charge density due to the initiator-derived radicals, which may
sultant latex particles are negatively charged. However, there are some cause some problems. For instance, low molecular weight emulsifiers
areas where positively charged latex particles are still needed such as would have a negative impact on nature of the film like water resistance
oil-field drilling [8], paper industries [9], fabric treatment [10–12], [23]. The introduction of polymerizable cationic monomers can effec-
protein adsorption [13] and coatings [14,15]. Cationic polymer latexes tively reduce the negative effect and the dosage of low molecular
prepared by emulsion polymerization have attracted wide interest re- weight emulsifiers. In recent years, with the development and the di-
cently, using cationic initiators and cationic emulsifiers such as cetyl versification of commercial cationic monomers, there are some litera-
trimethyl ammonium bromide (CTAB) [16–18], cetyl trimethyl am- ture on preparing cationic latexes by copolymerization of methacrylate,
monium chloride (CTAC) [19], and dodecyl trimethyl ammonium styrene, butyl acrylate, or their mixtures with different vinyl containing
bromide (DTAB) [20–22]. Kong et al. [16] found that zeta potential and amine or quaternary ammonium monomers [24–31]. The cationic
surface tension in the latex of styrene-butyl acrylate were directly re- monomers [(2-(acryloyloxy) ethyl) trimethyl ammonium chloride
lated with CTAB adsorption. Naves et al. [17] prepared cationic poly (AETMAC), (vinylbenzyl) trimethyl ammonium chloride (VBTMAC)
(methyl methacrylate) (PMMA) dispersions with high colloidal stability and methacrylatoethyl trimethyl ammonium chloride (DMC) with

⁎
Corresponding authors.
E-mail addresses: kmchen@sues.edu.cn (K. Chen), guoxuhong@ecust.edu.cn (X. Guo).

https://doi.org/10.1016/j.porgcoat.2020.105628
Received 13 December 2019; Received in revised form 27 February 2020; Accepted 28 February 2020
Available online 03 March 2020
0300-9440/ © 2020 Elsevier B.V. All rights reserved.
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

different pendent structure were employed to prepare core-shell ca-

tionic latex particles and compared [24]. Ramos et al. [25] reported
that more hydrophobic monomer VBTMAC showed higher conversion
than more hydrophilic monomer DMC at the same dosage when they
polymerized with styrene. Zhou and coworkers [28] prepared cationic
fluorinated polyacrylate emulsifier-free emulsions by RAFT emulsion
polymerization and obtained spherical-like particles with the diameter
of 44 nm–56 nm. Wang et al. [9] prepared cationic silicone-acrylic la-
texes with the particle size of approximately 75 nm and a narrow size
distribution in the presence of 0.5 % (w/w) DMC, which was suitable to Fig. 1. Chemical structures of different cationic monomers, (a) the general
the application of surface sizing agent. However, there is a lack of full structure of cationic comonomers, (b) various substituents on the nitrogen
study on the preparation and properties of cationic latexes using ca- atom.
tionic monomers with different substituents on the nitrogen atom.
Cationic latexes usually act as the binders in the filming process and shell phase. The specific synthetic route was shown in Scheme 1.
exist as the main matrix in the protective film during their application,
thus the selection of reactive monomers and the film properties are vital 2.2.1. Core phase
[32]. Methyl methacrylate (MMA) and butyl acrylate (BA), which are All emulsion polymerization reactions were carried out in a 250 mL
generally applied to the hard monomer and the soft monomer, re- four-necked round-bottomed flask fitted with a reflux condenser, two
spectively, are selected for copolymerizing with cationic comonomers. dropping funnels and a nitrogen inlet tube. The total weight of all
The stability of cationic latexes is remarkably inferior to that of the monomers was maintained at 15.5 g.
anionic latexes. However, previous cationic emulsion polymerization The 0.2 g CTAB, 50.0 g DI water and 1/5 of core monomers (1.4 g)
has rarely studied the stability of latexes, especially the alkali re- were introduced into the flask with the magnetic stirring rate of
sistance. 450 rpm. The mixed solution was heated to 75 °C in an oil bath after the
In this study, the effect of various substituents on the nitrogen atom pre-emulsifying for 15 min. Then the entire core initiator AIBI (0.1 g)
in cationic comonomer on the latex preparation, the stability and the dissolved in 8 g DI water was injected into the flask. The emulsion
film properties was systematically investigated. The cationic poly- polymerization was carried out at 75 °C for 30 min to get seed emulsion.
acrylate latex particles with core-shell structure were successfully syn- After that, the residual core monomers were added slowly through a
thesized by semi-continuous seeded emulsion polymerization, using a dropping funnel in 45 min. Finally, the flask was immersed in oil bath
cationic emulsifier CTAB, and a cationic initiator 2,2′-azobis[2-(2-imi- for another 1 h to obtain the core emulsion.
dazolin-2-yl)propane] dihydrochloride (AIBI). The cationic comonomer
DMC was employed in copolymerizing with MMA and BA, and com- 2.2.2. Shell phase
pared with 2-aminoethyl methacrylate hydrochloride (AEMH) and 2- In a typical experiment (Table 1), two solutions were prepared in
(dimethylamino)ethyl methacrylate (DMAEMA). A series of experi- separate flasks: one containing the 3.5 g MMA and 4.5 g BA, the other
ments demonstrated that the significant positive effect of the DMC containing 0.13 g AIBI and 0.5 g DMC dissolved in 8 g DI water. The
addition on the alkali resistance of the latex, and the deleterious effect solutions were dropped simultaneously into the flask within 1 h, re-
of excess residual initiator and emulsifier on water resistance of the spectively. After the completion of the addition, the whole system was
film. The structures and properties of cationic latexes and their films heated at 75 °C for another 1 h to ensure the polymerization was
were fully characterized by fourier transform infrared (FTIR), dynamic completed. Finally, the latex was cooled to room temperature and fil-
light scattering (DLS), transmission electron microscopy (TEM), differ- tered to obtain the cationic polyacrylate latex.
ential scanning calorimeter (DSC), contact angle goniometer (CA) and The process of preparing cationic polyacrylate latex using DMAEMA
tensile testing. or AEMH was the same as that using DMC.

2. Experimental 2.3. Characterization of cationic polyacrylate latex and its film

2.1. Materials The monomer conversion rate and coagulum content was de-
termined by gravimetric analysis method as in the following equations
Methyl methacrylate (MMA, 99.5 %) and butyl acrylate (BA, 99.5 (Eqs. (1) and (2)), respectively.
%) were purchased from Shanghai Aladdin Biochemical Technology
Co., Ltd. and stored at 4 °C prior to use after reduced pressure dis- m 0 (m2 − mc )/(m1 − mc ) − m4 + ma
monomer conversion= × 100%
tillation. All the other materials were used as received. m3
Methacrylatoethyl trimethyl ammonium chloride (DMC, 80 wt% in (1)
water), 2-aminoethyl methacrylate hydrochloride (AEMH, 90 %) and 2-
coagulum content= ma / m3 × 100% (2)
(dimethylamino)ethyl methacrylate (DMAMEA, 99 %) were obtained
from Adamas Reagent Co., Ltd. and stored at 4 °C in refrigerator. Cetyl Here, mc , m1, m2 were the mass of the container, the latex plus the
trimethyl ammonium bromide (CTAB, 99 %) and 2,2′-azobis[2-(2-imi- container, the latex plus the container after drying at 105 °C for 24 h,
dazolin-2-yl)propane] dihydrochloride (AIBI, 98 %) were obtained respectively. The m 0 , m3 , m4 , ma referred to the mass of the whole re-
from Macklin Inc. The water utilized in all experiments was distilled action system, the initial amount of monomers, the emulsifier and the
followed by deionization. The main structures of DMC, DMAEMA and coagula after drying.
AEMH are shown in Fig. 1. The average particle size and its distribution of the latex particles
were measured by dynamic light scattering (DLS) (Particle Sizer
2.2. Preparation of cationic polyacrylate latex Nicomp 380) at 25 °C. Samples were diluted to appropriate con-
centration and measured three times.
A typical recipe for preparing the cationic polyacrylate latex was The zeta potential value of the latex was obtained using Zeta
exhibited in Table 1. The mass ratios of the initiator, the emulsifier and Potential Nicomp 380 at 25 °C. The latex concentration used for the
the cationic comonomer were the mass ratios relative to the total measurement was diluted to approximately 0.2 wt%.
monomer mass. The latex was prepared in two steps: core phase and Fourier transform infrared (FT-IR) spectra of the samples were

2
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

Table 1
Typical recipe of cationic polyacrylate latex.
Core phase Shell phase CTAB/wt% DI water/g

MMA/g BA/g AIBI/wt% MMA/g BA/g DMC/g AIBI/wt%

3.5 3.5 0.66 3.5 4.5 0.5 0.84 1.3 66.0

Scheme 1. Synthetic route for preparing cationic polyacrylate latex particles.

Table 2 9 mm; width, 4 mm).

Latex properties with various AIBI dosage*.
Entry AIBI amount/ Monomer Coagulum Zeta potential/ 3. Results and discussion
wt% conversion/% content/% mV
3.1. Effects on preparation of cationic polyacrylate latex
1 0.5 97.58 0.10 52 ± 1
2 1.0 99.86 0.14 53 ± 2
3 1.5 100 0.03 56 ± 1
For the preparation of cationic latex, the amount of initiator and
4 2.0 100 0.04 55 ± 1 emulsifier, the type and dosage of cationic comonomer would influence
5 2.5 100 0.09 52 ± 1 the latex properties like the monomer conversion, the coagulum con-
tent, the zeta potential, the latex particle size and its distribution. The
* Reaction condition: CTAB dosage is 1.3 wt% and DMC dosage is 3.2 wt%, monomer conversion indicates the extent of reaction. The coagulum
respectively.
content and the zeta potential reveal the stability of the latex. The
particle size and its distribution would affect the film properties after
recorded between 4000 cm−1 and 400 cm−1 on a Nicolet 6700 spec-
application.
trophotometer using the attenuated total reflectance (ATR) technique.
The transmission electron microscopy (TEM) images of the cationic
3.1.1. The effect of initiator AIBI dosage
polyacrylate latex particles were taken with a JEM-1400 transmission
The effect of AIBI dosage on the latex properties was presented in
electron microscope at 200 kV operating voltage. Samples were diluted
Table 2. With increasing AIBI dosage, the monomer conversion in-
to proper concentration and the sample solution was putted by pipettes
creased gradually, and monomers reacted completely after increasing
to carbon grid and allowed to dry at room temperature.
AIBI dosage to 1.5 wt%. These can be explained by the conventional
The glass transition temperature (Tg) of the latex was measured by a
theory of emulsion polymerization. More free radicals would be pro-
DSC Q2000. The scanning rate was 10 °C/min from –40 °C to 100 °C
duced with increasing AIBI dosage in the aqueous phase. These free
under nitrogen atmosphere.
radicals would have more opportunities to diffuse into the micelles and
The contact angle (CA) measurements were performed on a JC2000
polymer latex particles, which were considered as the activation center,
contact angle goniometer by the sessile drop method with a micro-
causing an increase in monomer conversion [33]. The coagulum con-
syringe at room temperature. The static contact angle was obtained
tent decreased as AIBI dosage increased from 0.5 wt% to 1.5 wt%, and
from water droplets on the surface of the latex film. Three measure-
then increased slightly with further increasing AIBI dosage. This was
ments were performed for each sample to obtain mean value.
due to the increase in stability of the latex after introducing hydrophilic
The water absorption (WA) test of the film was carried out by im-
initiator AIBI, resulting in the decrease of the coagulum content.
mersing the film samples of the approximate dimensions 1 × 1 cm2 in
However, by further increasing AIBI dosage, the high decomposition
DI water at 25 °C for 48 h. The film was prepared by pouring the latex
rate of AIBI would promote the formation of coagula [34]. The zeta
into a Teflon mold and drying at 40 °C for 48 h. WA was given by
potential values were above +30 mV commonly associated with stable
WA= (w1 − w0)/ w0 × 100% (3) colloids.
The influence of AIBI dosage on the particle size and its poly-
where w0 , w1 were the sample weight before and after immersion for dispersity was shown in Fig. 2. The particle size decreased gradually
48 h, respectively. and had a narrow size distribution with the increase of AIBI dosage.
The alkali resistance of the latex was tested by adding 400 μL 1 M This could be ascribed to the increased concentration of free radicals in
NaOH solution to 2 mL latex to observe the latex stability. the aqueous phase by increasing AIBI dosage. The concentration of
The tensile strength was determined on a Hengyi HY-0580 testing oligomers increased, which were formed by the reaction of dissolved
instrument with a 100 N loading cell at a crosshead speed of 25 mm/ monomers in the aqueous phase. The oligomer would precipitate and
min. The samples were made into dumbbell shape (initial gauge length, absorb the emulsifiers dissolved in the aqueous phase to form a new

3
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

Fig. 2. The effect of AIBI dosage on particle size and size polydispersity. Fig. 3. The effect of CTAB dosage on particle size and size polydispersity.

latex particle after reaching a certain degree of polymerization. The Table 4

increase in the number of latex particles resulted in the decrease in the Latex properties with various DMC dosage*.
average particle size.
Entry DMC amount Monomer Coagulum Zeta potential
/wt% conversion/% content/% /mV
3.1.2. The effect of emulsifier CTAB dosage
10 0 100 0.62 54 ± 2
The effect of CTAB dosage on the latex properties were given in 11 1.3 100 0.18 55 ± 1
Table 3. The data indicated that the monomer reacted completely due 3 3.2 100 0.03 56 ± 1
to sufficient free radicals to trigger polymerization at AIBI dosage of 12 5.2 100 0.05 62 ± 2
1.5 wt%. The coagula decreased with increasing CTAB dosage. The 13 7.1 100 0.05 54 ± 3
14 9.0 100 0.02 50 ± 1
latex particles were unstable and easy to collide and aggregate to form
coagula due to the low coverage of CTAB on the particle surfaces when * Reaction condition: CTAB dosage is 1.3 wt% and AIBI dosage is 1.5 wt%,
the CTAB dosage was less than 1.3 wt%. Then the coverage of CTAB respectively.
was greatly increased with increasing CTAB dosage, resulting in a de-
crease in coagula. With increasing CTAB dosage, the zeta potential in- with increasing DMC dosage. The reduction in the coagula amount was
creased slightly initially, then decreased slightly after reaching a max- due to the increase in the stability of the latex caused by the addition of
imum value. This was believed to be a reflection of the increasing cationic comonomer. It was worth nothing that the zeta potential had a
proportion of CTAB formed micelles, which would increase the double maximum value at a DMC dosage of 5.2 wt%. From a theoretical point
layer potential difference and the zeta potential. However, the pro- of view, the zeta potential is the potential difference between the dis-
portion of CTAB formed micelles decreased with further increasing persion medium and the stationary layer of fluid attached to the dis-
CTAB dosage, more CTAB dissolved in the aqueous phase, causing the persed particles [16]. Thus, the zeta potential value depends on the
slight decrease in zeta potential [16]. charge density of the particles and the charge level in the bulk aqueous.
The effect of CTAB dosage on the particle size and its polydispersity A higher proportion of DMC participated in homopolymerization in the
was depicted in Fig. 3. It can be seen that the particle size of latex aqueous phase rather than copolymerization with shell monomers
particles decreased dramatically from 96 nm to 55 nm with increasing MMA and BA after the DMC consumption exceeded 5.2 wt%, causing
CTAB dosage. This can be explained that the nucleation mechanism of the decrease in potential difference between the aqueous phase and the
the emulsion polymerization with emulsifiers was micelle nucleation. stationary layer of fluid attached to the cationic latex particles. Similar
More micelles would form with increasing CTAB dosage, thus the latex phenomena were also observed by Wang et al. [9].
particle numbers increased, led to the decrease of average particle size The latex particle size and its polydispersity with different DMC
of latex particles [35]. Moreover, the latex particles had a narrow size dosage were shown in Fig. 4. A significant growth of the particle size
distribution in the range of CTAB dosages. with increasing DMC dosage from 0 wt% (without DMC) to 9.0 wt%
was observed. There are two possibilities of the particle size growth. On
3.1.3. The effect of cationic comonomer DMC dosage the one hand, the oligomeric radicals copolymerized with a higher
Table 4 showed the effect of DMC dosage on the latex properties. fraction of DMC units by increasing the DMC amount, which increased
The coagulum content decreased and the monomer reacted completely the solubility and the time needed for precipitation, and resulted in
increasing chances of being captured by existing particles [25]. On the
Table 3 other hand, the addition of the hydrophilic comonomer DMC to the
Latex properties with various CTAB dosage*. shell layer improved the hydrophilicity of the shell layer that allowed
the shell polymer chains to extend slightly towards the aqueous phase.
Entry CTAB Monomer Coagulum Zeta potential/
amount/wt% conversion/% content/% mV The high DMC dosage caused the more extendable polymer chains and
the larger particle size. All latexes prepared with different DMC levels
6 0.3 100 0.23 53 ± 1 had a narrow particle size distribution.
7 0.8 100 0.24 54 ± 1
3 1.3 100 0.03 56 ± 1
8 1.8 100 0.07 50 ± 1
9 2.3 100 0.06 53 ± 2
3.2. The effect of various substituents in cationic comonomers

* Reaction condition: AIBI dosage is 1.5 wt% and DMC dosage is 3.2 wt%, 3.2.1. FT-IR spectra
respectively. The chemical compositions of the cationic latex were characterized

4
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

were used to copolymerize with MMA and BA to form shell layer in the
same molar ratio (see Table 5). At the same molar concentrations of
cationic comonomers, latexes prepared by DMC and AEMH showed 100
% conversion rate, low coagulum content and narrow particle size
distribution, while the latex prepared by DMAEMA presented high
coagulum content and wide particle size distribution. These different
results were attributed to the thermo-responsive properties of
PDMAEMA. PDMAEMA was water soluble below the LCST (lower cri-
tical solution temperature) [36], however, it would turn to insoluble
above the LCST. At the reaction temperature of 75 °C, PDMAEMA
would change from hydrophilic to hydrophobic that would influence
the stability of the reaction system and cause massive coagula. The high
zeta potential of the latex prepared by DMAEMA could be attributed to
the higher protonation of DMAMEA under weak acidic conditions, re-
sulting in the higher positive charge density on the surfaces of the latex
particles. Therefore, DMAEMA would not be a good choice under the
reaction condition if stable and monodisperse latex particles were re-
Fig. 4. The effect of DMC dosage on particle size and size polydispersity.
quired.

3.2.3. Microscopic morphologies

TEM images of the representative samples of cationic polyacrylate
latex particles were exhibited in Fig. 6, which indicated that the par-
ticles were uniform spheres with diameter of ca. 70 nm. The well-de-
fined core-shell structure of the latex particles could be observed (Fig.
S1, Supporting Information) due to the difference in electron penetr-
ability of the core layer and shell layer. The dark and light regions in
the particles corresponded to the polyacrylate core layer and cationic
comonomer containing polyacrylate shell layer, respectively. Mean-
while, the particle size observed by TEM accorded with the results from
dynamic light scattering.

3.2.4. Thermal properties

The critical parameter concerning thermal properties, Tg, was de-
termined for DMC, DMAEMA, and AEMH containing cationic latexes as
well as the P(MMA-BA) core latex using differential scanning calori-
metry (DSC). The DSC curves were shown in Fig. 7. Typically, the Tg
values of PMMA and PBA are 105 °C and−47 °C, respectively [37]. The
Fig. 5. FT-IR spectra of latexes with different cationic comonomers: (a) DMC; theoretical Tg values of the core layer and the shell layer (without
(b) DMAEMA; (c) AEMH. considering the effect of the cationic comonomer dosage on Tg) were
calculated using the well-known Fox equation [38], and the calculation
by FT-IR spectroscopy and the results were presented in Fig. 5. All FT-IR results were 9.9 °C and 1.3 °C, respectively. From Fig. 7, it was observed
spectra exhibited the characteristic stretching peaks of CeH (CH2) at that the Tg of core layer measured by DSC was significantly higher than
2955 and 2873 cm−1, the stretching peaks of C]O at 1725 cm−1 and the theoretical value, which was also reported by Schmid and cow-
the distortion vibration peaks of CH2 at 1449 and 1385 cm−1. The orkers [39]. Another phenomenon should be noticed is that the cationic
peaks at 1142 cm−1 were the CeN absorption peak. The bands at polyacrylate latex had only one Tg, nevertheless, the TEM images
3397 cm−1 (νN-H) originated from AEMH were found in the FT-IR manifested a clear core-shell structure for the prepared latex particles.
spectrum while no characteristic stretching peaks of NeH was found in This phenomenon may be ascribed to the tiny difference between the Tg
the FT-IR spectrum of the latexes with DMC and DMAEMA. The results of the core phase and the shell phase.
corresponded to the chemical structures of the three different cationic
comonomers and indicated all monomers took part in the copolymer- 3.3. Stability of cationic polyacrylate latex
ization.
Due to the positively charged latex particles, cationic latexes were
3.2.2. Latex properties generally considered to have poor alkali resistance. However, little
Three diverse cationic comonomers (quaternary ammonium salt literature had studied the effect of cationic comonomers on the alkali
DMC, tertiary amine DMAEMA, primary amine hydrochloride AEMH) resistance of cationic latexes. Here, the effect of cationic comonomers

Table 5
Latex properties with various cationic comonomers*.
Entry Cationic comonomer Monomer conversion/% Coagulum content/% Zeta potential/mV pH Particle size/nm PDI

12 DMC 100 0.05 62± 2 3.47 77.5± 0.6 0.051±0.009

15 DMAEMA 99.47 1.95 65± 1 6.92 76.3± 0.4 0.239±0.010
16 AEMH 100 0.16 60± 1 3.86 73.1± 0.4 0.071±0.007

* Reaction condition: CTAB dosage is 1.3 wt%, AIBI dosage is 1.5 wt%, and DMC dosage is 5.2 wt%, respectively. The molar ratio of the cationic comonomer is
kept the same in the recipe.

5
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

Fig. 6. TEM images of core-shell latex particles using different cationic comonomers. (a) DMC; (b) DMAEMA; (c) AEMH.

repulsion. The stability of latexes decreased and floccules occurred.

However, the alkali resistance of latexes was improved after increasing
DMC dosage to a high content. Therefore, the alkali resistance of ca-
tionic latexes could be controlled simply and feasibly by adjusting DMC
dosage.

3.3.2. The effect of various substituents on the nitrogen atom of cationic

comonomers
To investigate the alkali resistance of latexes prepared by different
cationic comonomers, a series of experiments were carried out and the
results were illustrated in Fig. 9. With the same molar concentration of
cationic comonomers, all of the three latexes exhibited deprived alkali
resistance. The latexes prepared by DMC showed slightly better alkali
resistance than the latexes prepared by DMAEMA or AEMH, no floc-
cules occurred after adding NaOH solution for 5 min. However, serious
floccules occurred after standing for 24 h. All these phenomena could
be explained by the DLVO theory. DMC was charged by the quaternary
ammonium group. DMAEMA was charged by the protonation of its
tertiary amine group. AEMH was charged by the hydrochloride. After
Fig. 7. DSC curves of the film with different cationic comonomer: (a) DMC adding NaOH solution, the protonation of DMAEMA was inhibited, the
(Table 5, 12); (b) DMAEMA (Table 5, 15); (c) AEMH (Table 5, 16); (d) P(MMA- positive charge density of latex particles using AEMH decreased due to
BA) core. acid-base neutralization. Thus the latexes prepared by DMAEMA or
AEMH showed poorer alkali resistance than the latexes prepared by
on the alkali resistance was investigated. DMC.

3.4. Film properties

3.3.1. The effect of DMC dosage
The effect of DMC dosage on the alkali resistance of cationic latexes In the practical application of cationic latexes, they usually acted as
was portrayed in Fig. 8. The latexes without or with low DMC contents the binder in the filming process and then existed as the film. Therefore,
were corresponded to previous perception that the cationic latexes had it was of great significance to study the water resistance and the me-
poor alkali resistance. An enormous amount of floccules occurred im- chanical properties of the formed film.
mediately after adding NaOH solution. However, the alkali resistance
was improved significantly after increasing DMC dosage to a relatively 3.4.1. Water resistance
high content (9.0 wt%), no floccules occurred after adding NaOH so- Water resistance could be characterized by water absorption rate
lution for 5 min and after standing for 24 h, which was not consistent mentioned elsewhere [28]. And the water contact angle was commonly
with the previous cognition. When DMC dosage was increased to 5.2 wt used as a criterion for the evaluation of the hydrophobicity of the film
%, the latex became opaque rapidly, but no floccules produced after and a reflection of the surface properties of the film [35,41]. The water
5 min. The latex flocculated seriously after standing for 24 h. The above absorption rate and the water contact angle of the latex film with re-
phenomena indicated that the addition of a large amount of DMC could lated factors were evaluated and the results were shown in Fig. 10.
improve the alkali resistance of latexes dramatically. It can be observed from Fig. 10(a) that the water absorption rate of
This phenomenon could be explained by the classical DLVO the film increased from 38.9 %–82.3 % as AIBI dosage increased from
(Darjaguin Landan Verwey Overbeek) theory [40]. The stability of the 0.5 wt % to 2.5 wt %. The increase was attributed to the increasing
latex system was governed by a balance between two forces, namely hydrophilic residual initiator AIBI in the film. The film would be more
van der Waals attractive force and the electrostatic repulsion, which hydrophilic with more AIBI used and existed in the film. This ex-
ensured the latex particles are hard to get close and coalesce. In this planation was verified by the change in contact angle shown in
experiment, there were a large amount of positive charges on the latex Fig. 10(a1). The contact angle of the film decreased from 80.8 ° to 69.0
particles, and the addition of NaOH solution provided massive counter ° with increasing AIBI dosage gradually.
ions. These counter ions would diffuse to the surface of latex particles As shown in Fig. 10(b), the water absorption rate of the film in-
for charge neutralization, resulting in the reduction in the electrostatic creased from 44.5 %–80.3 % with the increase of CTAB dosage from

6
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

Fig. 8. The effect of DMC dosage on alkali resistance. (a0) to (d0) were optical images of latexes with 0, 1.3 wt%, 5.2 wt%, 9.0 wt% DMC, respectively; (a1) to (d1)
were optical images after adding NaOH solution for 5 min, respectively; (a2) to (d2) were optical images after standing for 24 h, respectively.

Fig. 9. The effect of different cationic comonomers on alkali resistance. (a0) to (c0) were optical images of latexes with DMC, DMAEMA, AEMH, respectively; (a1) to
(c1) were optical images after adding NaOH solution for 5 min, respectively; (a2) to (c2) were optical images after standing for 24 h, respectively.

7
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

Fig. 10. The effect of different factors on the water absorption rate and the contact angle of the film, (a) and (a1) AIBI dosage; (b) and (b1) CTAB dosage; (c) and (c1)
DMC dosage; (d) and (d1) different cationic comonomers.

8
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

0.3 wt% to 2.3 wt%. The increase might be due to the presence of more sacrificing elongation at break (795 %). The superior mechanical
hydrophilic groups on CTAB on the surface of the film during the film properties of the film prepared by copolymerization with AEMH might
forming process. The result was consistent with the water contact angle be due to the hydrogen-bond interaction between the polymer segments
of the film. With more CTAB used, the contact angle of the film declined containing AEMH [42]. The above phenomena indicated that AEMH
from 95.0 ° to 49.5 ° . Excessive initiator and emulsifier residue would was the best choice among the three cationic comonomers to improve
deteriorate the water resistance of the film. the mechanical properties of the film, DMAEMA was the worst choice,
The water absorption trend of the film with increasing DMC con- and DMC was in the middle.
sumption was portrayed in Fig. 10(c). It can be seen that the water
absorption of the film increased from 48.9 %–87.3 % with increasing 4. Conclusions
DMC dosage from 1.3 wt% to 9.0 wt%. With more hydrophilic
monomer DMC copolymerizing with the shell monomers, the shell layer In this work, we prepared a series of cationic polyacrylate latexes
was more hydrophilic. During the film forming process, part of the via semi-continuous seeded emulsion polymerization from MMA and
hydrophilic groups would migrate to the surface of the film. There BA in the presence of a small amount of cationic comonomer. With
existed the affinity action between the hydrophilic group on the film increasing AIBI dosage, the monomer conversion, the water absorption
surface and water, causing an increment in water absorption [26]. The rate of the film increased gradually while the coagulum content and the
contact angle trend of the film with DMC amount (as shown in water contact angle decreased. With increasing CTAB dosage, the coa-
Fig. 10(c)) showed a contrary tendency of the water absorption rate. gulum content, the particle size and the water contact angle decreased
The higher the hydrophilic monomer used, the higher the water ab- gradually, meanwhile, the water absorption rate increased. The particle
sorption rate and the smaller the contact angle. The water contact an- size and the water absorption rate increased with increasing DMC do-
gles were low if no cross-linking agent or fluorine-containing modifier sage, whereas the coagulum content and the water contact angle de-
was used, similar to the results proposed by Zhou et al. [28]. creased. The addition of cationic comonomer DMC could effectively
The effect of different cationic comonomers on the water absorption improve the alkali resistance of the latex, especially in high DMC
rate and the contact angle was investigated and shown in Fig. 10(d) and content. However, it failed to show the same effect after adding the
(d1). A low water absorption rate and a high contact angle were ob- same molar amount of DMAEMA and AEMH. This highlights the in-
served in the test of the film prepared by DMAEMA containing latex. A fluence of different charge modes of cationic latex particles on the alkali
possible explanation was that the hydrophilicity of DMAEMA under resistance of the emulsion. The stability mechanism was well explained
LCST was due to its protonation. However, the protonation of DMAEMA by the DLVO theory. The addition of AEMH improved the tensile
was restricted after the filming process, and its hydrophilicity de- strength of the film effectively without sacrificing the elongation at
creased, showing more hydrophobicity. break. While the addition of DMC could improve the tensile strength of
the film by sacrificing some degree of the elongation at break. As ca-
3.4.2. Mechanical properties tionic polyacrylate latex was found to have satisfactory film forming
The mechanical properties of the cationic polyacrylate film were ability and excellent mechanical properties, this latex would have po-
presented in Fig. 11. As shown in Fig. 11(a), the stress at break of the tential application in wood paint as the primer.
film increased notably from 5.03 MPa to 9.83 MPa with increasing DMC
dosage from 1.3 wt% to 9.0 wt%, while the elongation at break de- CRediT authorship contribution statement
creased from 1132 % to 533 %. This could be ascribed to the increase in
hard monomer DMC dosage. It could be seen that the addition of DMC Chen Hua: Data curation, Software, Writing - original draft, Writing
could improve the tensile strength of the cationic polyacrylate film - review & editing. Kaimin Chen: Conceptualization, Methodology,
dramatically with sacrificing some degree of the elongation at break. Software, Validation, Writing - review & editing, Project administra-
The stress-strain curves of the cationic polyacrylate film with dif- tion. Zun Wang: Software. Xuhong Guo: Conceptualization,
ferent cationic comonomers were exhibited in Fig. 11(b). The stress- Resources, Supervision, Funding acquisition.
strain curves suggested a marked difference between three different
polyacrylate films with DMC, DMAEMA, AEMH, respectively. Poly- Declaration of Competing Interest
acrylate film using DMAEMA exhibited the minimum elongation (672
%) and stress (5.36 MPa) at break. Nevertheless, polyacrylate film using The authors declare that they have no known competing financial
AEMH exhibited the maximum stress at break (9.83 MPa), without interests or personal relationships that could have appeared to

Fig. 11. Mechanical properties of the cationic polyacrylate film, (a) stress-strain curves of polyacrylate film with different DMC dosage; (b) stress-strain curves of
polyacrylate film with different cationic comonomers.

9
C. Hua, et al. Progress in Organic Coatings 143 (2020) 105628

influence the work reported in this paper. with poly(methyl methacrylate), ACS Appl. Mater. Interfaces 3 (6) (2011)
1933–1939.
[19] K. Land fester, N. Bechthold, F. Tiarks, A. M, Miniemulsion polymerization with
Acknowledgements cationic and nonionic surfactants: a very efficient use of surfactants for heterophase
polymerization, Macromolecules 32 (1999) 2679–2683.
The authors are grateful for the financial supports of this study by [20] M. Antonietti, W. Bremser, D. Mueschenborn, C. Rosenauer, B. Schupp, M. Schmidt,
Synthesis and size control of polystyrene latices via polymerization in microemul-
National Natural Science Foundation of China (No. 5171101370). sion, Macromolecules 24 (25) (1991) 6636–6643.
[21] M. Bradley, F. Grieser, Emulsion polymerization synthesis of cationic polymer latex
Appendix A. Supplementary data in an ultrasonic field, J. Colloid Interface Sci. 251 (1) (2002) 78–84.
[22] I. Katime, J. Arellano, P. Schulz, Poly(n-hexyl methacrylate) polymerization in
three-component microemulsion stabilized by a cationic surfactant, J. Colloid
Supplementary material related to this article can be found, in the Interface Sci. 296 (2) (2006) 490–495.
online version, at doi:https://doi.org/10.1016/j.porgcoat.2020. [23] X. Cui, S. Zhong, H. Wang, Emulsifier-free core–shell polyacrylate latex nano-
particles containing fluorine and silicon in shell, Polymer 48 (25) (2007)
105628.
7241–7248.
[24] N.V. Dziomkina, M.A. Hempenius, G.J. Vancso, Synthesis of cationic core-shell latex
References particles, Eur. Polym. J. 42 (1) (2006) 81–91.
[25] J. Ramos, J. Forcada, The role of cationic monomers in emulsion polymerization,
Eur. Polym. J. 46 (5) (2010) 1106–1110.
[1] F. Wang, L. Guo, T. Qiu, J. Ye, L. He, X. Li, A direct polymerization approach toward [26] L.J. Chen, Effect of cationic monomer on properties of fluorinated acrylate latex,
hindered phenol/polymer composite latex and its application for waterborne Chin. Chem. Lett. 23 (6) (2012) 736–740.
damping coating, Prog. Org. Coat. 130 (2019) 1–7. [27] D.-J. Voorn, W. Ming, A.M. van Herk, Control of charge densities for cationic latex
[2] S. Nuasaen, P. Tangboriboonrat, Optical properties of hollow latex particles as particles, Macromolecules 38 (9) (2005) 3653–3662.
white pigment in paint film, Prog. Org. Coat. 79 (2015) 83–89. [28] X.C. Jianhua Zhou, Jianzhong Ma, Cationic fluorinated polyacrylate emulsifier-free
[3] H.E. Nasr, S.M. Sayyah, D.M. Essa, S.H. Samaha, A.M. Rabie, Utilization of acrylates emulsion mediated by poly(2-(dimethylamino) ethyl methacrylate)-b-poly(hexa-
emulsion terpolymer with chitosan as a finishing agent for cotton fabrics, fluorobutyl acrylate) trithiocarbonate via ab initio RAFT emulsion polymerization,
Carbohydr. Polym. 76 (1) (2009) 36–45. Prog. Org. Coat. 100 (2016) 86–93.
[4] M. Li, W. Liu, Q. Zhang, S. Zhu, Mechanical force sensitive acrylic latex coating, [29] W. Xu, Q. An, L. Hao, Z. Sun, W. Zhao, Synthesis and characterization of cationic
ACS Appl. Mater. Interfaces 9 (17) (2017) 15156–15163. fluorinated polyacrylate soap-free latexes with core-shell structure, J. Polym. Res.
[5] R.S. Tığlı, V. Evren, Synthesis and characterization of pure poly(acrylate) latexes, 20 (2) (2013).
Prog. Org. Coat. 52 (2) (2005) 144–150. [30] W. Xu, Q. An, L. Hao, L. Huang, Synthesis, film morphology, and performance of
[6] J.P. Pinheiro, L. Moura, R. Fokkink, J.P. Farinha, Preparation and characterization cationic fluorinated polyacrylate emulsion with core-shell structure, J. Appl. Polym.
of low dispersity anionic multiresponsive core-shell polymer nanoparticles, Sci. 125 (3) (2012) 2376–2383.
Langmuir 28 (13) (2012) 5802–5809. [31] S. Gu, L. Duan, X. Ren, G.H. Gao, Robust, tough and anti-fatigue cationic latex
[7] B. Liu, M. Zhang, G. Wu, H. Zhang, Synthesis of large-scale, monodisperse latex composite hydrogels based on dual physically cross-linked networks, J. Colloid
particles via one-step emulsion polymerization through in situ charge neutraliza- Interface Sci. 492 (2017) 119–126.
tion, Colloids Surf. A Physicochem. Eng. Asp. 500 (2016) 127–136. [32] H. Wang, L. Tang, X. Wu, W. Dai, Y. Qiu, Fabrication and anti-frosting performance
[8] G.A. Al-Muntasheri, I.A. Hussein, H.A. Nasr-El-Din, M.B. Amin, Viscoelastic prop- of super hydrophobic coating based on modified nano-sized calcium carbonate and
erties of a high temperature cross-linked water shut-off polymeric gel, J. Petrol. Sci. ordinary polyacrylate, Appl. Surf. Sci. 253 (22) (2007) 8818–8824.
Eng. 55 (1-2) (2007) 56–66. [33] L. Chen, F. Wu, Preparation and characterization of pure polyacrylate polymer
[9] Y. Wang, S. Fang, Preparation and characterization of cationic silicone-acrylic latex colloid through emulsion polymerization using a novel initiator, Colloids Surf. A
surface sizing agent, Prog. Org. Coat. 88 (2015) 144–149. Physicochem. Eng. Asp. 392 (1) (2011) 300–304.
[10] J. Zhou, X. Chen, J. Ma, Synthesis of cationic fluorinated polyacrylate copolymer by [34] S. Suzuki, K. Kikuchi, A. Suzuki, T. Okaya, M. Nomura, Effect of chain transfer
RAFT emulsifier-free emulsion polymerization and its application as waterborne agents on the kinetics and mechanism of particle nucleation in the emulsion
textile finishing agent, Dye. Pigment. 139 (2017) 102–109. polymerization of vinyl pivalate, Colloid Polym. Sci. 285 (5) (2006) 523–534.
[11] D. Gao, J. Feng, J. Ma, B. Lü, J. Lin, J. Zhang, Synthesis of cationic binder through [35] J.-W. Ha, I.J. Park, S.-B. Lee, Hydrophobicity and sliding behavior of liquid droplets
surfactant-free emulsion polymerization for textile pigment applications, Prog. Org. on the fluorinated latex films, Macromolecules 38 (3) (2005) 736–744.
Coat. 77 (11) (2014) 1834–1840. [36] J.-T. Sun, Z.-Q. Yu, C.-Y. Hong, C.-Y. Pan, Biocompatible zwitterionic sulfobetaine
[12] J. Lin, X. Chen, C. Chen, J. Hu, C. Zhou, X. Cai, W. Wang, C. Zheng, P. Zhang, copolymer-coated mesoporous silica nanoparticles for temperature-responsive drug
J. Cheng, Z. Guo, H. Liu, Durably antibacterial and bacterially antiadhesive cotton release, Macromol. Rapid Commun. 33 (9) (2012) 811–818.
fabrics coated by cationic fluorinated polymers, ACS Appl. Mater. Interfaces 10 (7) [37] Y. Liu, W. Schroeder, M. Soleimani, W. Lau, M.A. Winnik, Effect of hyperbranched
(2018) 6124–6136. poly(butyl methacrylate) on polymer diffusion in poly(butyl acrylate-co-methyl
[13] J. Cao, X. Pan, W. Huang, Y. Wang, D. Hua, X. Zhu, H. Liang, Synthesis of cationic methacrylate) latex films, Macromolecules 43 (15) (2010) 6438–6449.
poly(4-vinylpyridine)-functionalized colloidal particles by emulsion polymerization [38] L.J. Chen, H.X. Shi, H.K. Wu, J.P. Xiang, Preparation and characterization of a novel
with reactive block copolymer for protein adsorption, J. Colloid Interface Sci. 381 fluorinated acrylate resin, J. Fluorine Chem. 131 (2010) 731–737.
(1) (2012) 137–142. [39] A. Schmid, P. Scherl, S.P. Armes, C.A.P. Leite, F. Galembeck, Synthesis and char-
[14] K. Feng, X. Li, L. Yu, Synthesis, antibacterial activity, and application in the anti- acterization of film-forming colloidal nanocomposite particles prepared via sur-
fouling marine coatings of novel acylamino compounds containing gramine groups, factant-free aqueous emulsion copolymerization, Macromolecules 42 (11) (2009)
Prog. Org. Coat. 118 (2018) 141–147. 3721–3728.
[15] B. Wang, F. Wang, Y. Kong, Z. Wu, R.-M. Wang, P. Song, Y. He, Polyurea-cross- [40] T. Yin, Z. Yang, M. Lin, J. Zhang, Z. Dong, Aggregation kinetics and colloidal sta-
linked cationic acrylate copolymer for antibacterial coating, Colloids Surf. A bility of amphiphilic Janus nanosheets in aqueous solution, Ind. Eng. Chem. Res. 58
Physicochem. Eng. Asp. 549 (2018) 122–129. (11) (2019) 4479–4486.
[16] X.Z. Kong, X. Zhu, X. Jiang, X. Li, Preparation and full characterization of cationic [41] B. Zhang, B. Liu, X. Deng, S. Cao, X. Hou, H. Chen, A novel approach for the pre-
latex of styrene–butyl acrylate, Polymer 50 (17) (2009) 4220–4227. paration of organic-siloxane oligomers and the creation of hydrophobic surface,
[17] A.F. Naves, R.R. Palombo, L.D. Carrasco, A.M. Carmona-Ribeiro, Antimicrobial Appl. Surf. Sci. 254 (2) (2007) 452–458.
particles from emulsion polymerization of methyl methacrylate in the presence of [42] X. Dai, Y. Zhang, L. Gao, T. Bai, W. Wang, Y. Cui, W. Liu, A. Mechanically Strong,
quaternary ammonium surfactants, Langmuir 29 (31) (2013) 9677–9684. Highly Stable, Thermoplastic, and Self-Healable Supramolecular Polymer Hydrogel,
[18] L.D. Melo, R.R. Palombo, D.F. Petri, M. Bruns, E.M. Pereira, A.M. Carmona-Ribeiro, Adv. Mater. 27 (23) (2015) 3566–3571.
Structure-activity relationship for quaternary ammonium compounds hybridized

10