Journal of Molecular Liquids 317 (2020) 114136

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Journal of Molecular Liquids

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Influence of the hydrophilic moiety of polymeric surfactant on their

surface activity and physical stability of pesticide suspension concentrate
Shupeng Zhang a, Xiaodong Yang a, Zhenbei Tu b, Wendong Hua b, Penghui He b, Haihui Li b,
Bo Zhang b,⁎, Tianrui Ren b,⁎
a
State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering/Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou
University, Guiyang 550025, PR China
b
The Key Laboratory of Resource Chemistry of Ministry of Education, College of Chemistry and Materials Science, Shanghai Normal University, 100 Guilin Road, Shanghai 200234, PR China

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

Article history: Polymeric surfactant has explored as an efficient dispersant for improving the physical stability of pesticide sus-
Received 12 June 2020 pension concentrate. However, the influence of the hydrophilic monomer on the surface-active property of poly-
Received in revised form 17 August 2020 meric surfactant and its application performance in pesticide formulation is rare investigated. Herein, three kinds
Accepted 23 August 2020
of random polymers were designed and synthesized via polymerization reaction of styrene (St), methacrylic acid
Available online 24 August 2020
(MAA) with 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA) and vinyl sulfonate sodium (VS),
Keywords:
respectively. A series of surface-active parameters, including critical aggregation concentration (CMC), saturation
Polymeric surfactant surface excess concentration (Γmax), minimum area per molecule (Amin) and standard Gibbs free energy ΔG0m
Surface activity values were obtained from surface tension measurement. The results showed that CMC increased and ΔG0m de-
Dispersant creased with the increase of the hydrophilicity of the third monomer. The results of foamability measurement in-
Pesticide dicated that the polymeric surfactant with VS as the third monomer had the best foam producing ability and foam
Suspension concentrate stability. When HPA served as the third monomer, the surfactant had the lowest hydrophile lipophile balance
(HLB) value and the O/W emulsion prepared by it had the worst stability. Besides, the influence of synthesized
polymeric surfactants as dispersant on zeta potential, viscosity and suspension rate of 430 g/L tebuconazole sus-
pension concentrate were investigated. The results showed that poly(styrene-co-methacrylic acid-co-2-hy-
droxypropyl acrylate) performed best in improving the physical stability of the formulations. From SEM
imagines of tebuconazole particle, it was found the increase of particle size in tebuconazole suspension concen-
trate were caused by aggregation or Ostwald ripening after thermal storage.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction block length is much less pronounced [5]. Therefore, researches are
mainly focused on the influence of the hydrophobic segment [6]. In
Amphiphilic copolymer, as a particular type of surfactant, has been this respect the influence of the nature and topology of the hydrophilic
extensively employed as dispersant and can be found in formulations moieties, even being crucial parameters for their properties, is still lack-
for coatings, paints, agrochemical, etc. [1–3]. The simultaneous presence ing in the open literatures. Indeed, Garnier S et al., when working on
of both hydrophilic and hydrophobic parts in the same molecule has several different copolymers with the same hydrophobic block (butyl
been recognized as the key feature and responsible for their character- acrylate) but a significantly different hydrophilic one, clearly observed
istic properties in solution, which includes adsorption at interface and that the aggregation behavior, as shown by the CMC values, as well as
self-assembly into a variety of micellar aggregates [4]. Compared to the surface activity of these copolymers were mainly determined by
low-molecular weight ones, polymeric surfactant is bound to numerous the chemical structure of the hydrophilic block [7].
surface site at the same time forming durable adsorption layers on the Recently, polymeric surfactant, as an efficient and multifunctional
particles and improve the stabilization of their suspension concentrate water soluble polymer with the advantages of low dosage and strong
by two basic mechanism, electrostatic stabilization and steric stabiliza- adsorbability, has been used as dispersant in pesticide water-based for-
tion [1,4]. It is well known that the surface activity and self- mulations to solve some problems, such as aggregation, coalescence,
assembling property of polymeric surfactant are strongly depended on flocculation and Ostwald ripening, which reduce the stability and effi-
the hydrophobic moieties, while the dependence from the hydrophilic cacy of the active ingredients [3,8,9]. By adsorbing on the surface of
the pesticide particle to form an electric double layer, they are expected
⁎ Corresponding authors. to improve the dispersibility and stability of formulation. To the best of
E-mail addresses: zb830216@[Link] (B. Zhang), trren@[Link] (T. Ren). our knowledge, there are still rare literatures focusing on the

[Link]
0167-7322/© 2020 Elsevier B.V. All rights reserved.
2 S. Zhang et al. / Journal of Molecular Liquids 317 (2020) 114136

relationship between the structure of the hydrophilic moieties of poly- for 5 h at 80 °C with an oil bath. After cooling down to room tempera-
meric surfactant and its effect mechanism of pesticide particles in for- ture, the reaction solution was neutralized to pH 7–8 with 30 wt%
mulation. Therefore, it is still interesting and urgent to improve the NaOH solution. Then white crude product was obtained with a spray
understanding of the influence of the hydrophilic segment in polymeric dryer. After dissolved in deionized water, the crude product was dia-
surfactant on its surface activity and application in pesticide lyzed via a dialysis membrane (nominal molar mass cut off 1000) to re-
formulation. move the low-molar-mass molecules. Replaced the deionized water per
In this paper, three random copolymeric surfactants were synthe- 3 h until the conductivity of dialysate close to the conductivity of deion-
sized by copolymerization of two common monomers (styrene and ized water. The pure product was obtained after the water was removed
methacrylic acid) with different third monomers (2-hydroxyethyl acry- with a freeze dryer.
late, 2-hydroxypropyl acrylate and vinyl sulfonate, sodium salt). The
surface activity, foamability and emulsifying property of three poly- 2.2.2. Preparation of 430 g/L tebuconazole SC
meric dispersants were investigated. Moreover, by using as dispersant 430 g/L tebuconazole SC was prepared by the wet milling process ac-
in high-concentrated tebuconazole SC, the influence of three polymeric cording to the formulation: 38 ± 2 wt% active ingredient, 1 wt%-8 wt%
dispersants on the suspension rate, zeta potential, viscosity and thermal polymeric surfactant, 5 wt% anti-freezing agent ethylene glycol, 0.2 wt
storage stability of tebuconazole SC was studied and compared to deter- % xanthan gum, 0.3 wt% silicone antifoam and water added up to a
mine the relationship between the performance (stabilization mecha- total amount of 100 wt%. The mixture was milled for 1 h at 1200 rpm
nism) and the structure of the hydrophilic monomers. in a sand mill filled with zirconia beads. Then the obtained product
was divided into two parts and stored under different conditions for
2. Materials and methods two weeks: room temperature and 54 °C. The viscosity, zeta potential,
suspension rate and particle size (D90) of samples were measured be-
2.1. Materials fore and after storage.

Styrene (St), methacrylic acid (MAA), 2-hydroxyethyl acrylate

(HEA), 2-hydroxypropyl acrylate (HPA), vinyl sulfonate, sodium salt 2.3. Measurements
(VS), methanol, ethylene glycol, cottonseed oil, turpentine, liquid paraf-
fin and isopropyl alcohol were analytical reagent and obtained from 2.3.1. The gel permeation chromatograph (GPC) test
Sinopharm Chemical Reagent Co., Ltd. (China). Ammonium persulfate, The Mn, Mw and Mw/Mn of three polymeric surfactants were tested
sodium hydroxide, toluene and o-dichlorobenzene were chemical re- on a LC98II-RI gel permeation chromatograph (GPC) (Beijing WENFEN
gent and obtained from Aladdin. Xanthan gum was food regent grade Analytical Instrument Development Co. (Beijing, China)) with three
and purchased from Shanghai Jihu Chemical Co., Ltd. (Shanghai, SB-803HQ styragel columns (Shodex) and Shodex RI-201H refractive
China). Tebuconazole (97.6%) was from Jiangsu Yangnong Chemical index detector. Phosphate buffer with pH = 7.2 (56 mM NaH2PO4/
Group Co., Ltd. (Jiangsu, China). 144 mM Na2HPO4/300 mM NaCl) was used as eluent at a flow rate of
0.3 mL/min at 30 °C.
2.2. Preparation
2.3.2. Fourier transform infrared (FT-IR) spectra
2.2.1. Synthesis of polymeric surfactant Fourier transform infrared (FT-IR) spectra was carried out with a
The random polymeric surfactants were synthesized by free radical Thermo Scientific Nicolet 6700 IR spectrophotometer over the fre-
polymerization of St, MAA with HEA, HPA and VS according to Scheme quency range of 4000-500 cm−1. The samples were pressed with KBr
1, and donated as SM-HEA, SM-HPA and SM-VS, respectively [10,11]. powders.
The mole ratio of St: MAA: HEA/HPA/VS was 1:4:1. Methanol as solvent
and ((NH4)2S2O8/NaHSO3) aqueous solution were added into a 250-mL 2.3.3. H-nuclear magnetic resonance (1H NMR)
1
four-necked flask equipped with a condenser. Then three monomers H NMR measurement was carried out using a Bruker AvanceIII 400
were dropped into the flask simultaneously. The reaction conducted spectrometer at 400 MHz with DMSO‑d6 as solvent.

Scheme 1. Preparation scheme of SM-HEA, SM-HPA, SM-VS.

 S. Zhang et al. / Journal of Molecular Liquids 317 (2020) 114136 3

2.3.4. Surface tension measurement the emulsion was poured into a 100 mL cylinder. Initially, the emulsions
The surface tension was operated at 25 °C with a Wilhelmy plate, were within “homogeneous phase” before they start to break. As the
using a BZY-1 automatic surface tensiometer [12]. The Gibbs' law was separation start, the emulsion formed the transparent layer in the
used to calculate the adsorption and aggregation data of the polymeric water/oleic phase. The volume proportion of the separated water and
surfactants in water [13]. According to Gibbs' law, the saturation surface oleic phases kept changing until the emulsified layer reached a plateau.
excess concentrations (Γmax) and the minimum area per molecule The separation time when the emulsified plateau was less than 5% of the
(Amin) values were calculated by the Gibbs adsorption isotherm equa- total volume was recorded.
tion (Eqs. (1) and (2)) [14].
   2.3.8. Suspension rate
−1 dγ The suspension rate was measured according to the national stan-
Γmax ¼ ð1Þ
nRT d ln C dard of China GB/T14825-2006. 2.5 g sample of 430 g/L tebuconazole
SC sample was added into a 250 mL measuring cylinder with a stopper.
1014 Next, the formulation was diluted to 250 mL with deionized water and
Amin ¼ ð2Þ
NΓmax the cylinder was inverted up and down for 30 times to ensure uniform
mixing in 1 min. After 30 min, 225 mL diluent was taken out using a
where dγ/d lnC is the maximum slope, γ is the surface tension (mN/m), straw from top to bottom. Then the remaining liquid was transferred
T is the absolute temperature, R is the gas constant (8.314 J/mol·K). The into a clean petri dish (m1). After dried under vacuum at 70 °C for
value of n depends critically on the valence or stoichiometry of charge 24 h, the petri dish was weighed again (m2). The suspension rate
neutralization of the air–water interface (n = 1) [15]. C is the concentra- ω(%) was calculated using Eq. (4).
tion(mol/L), N is Avogadro's number, Γmax is in mol/m2, Amin is in nm2.
The standard Gibbs free energy ΔG0m of adsorption was calculated 2:5∗A−ðm2 −m1 Þ 10
ω¼   100 ð4Þ
using Eq. (3) [16]. 2:5∗A 9

ΔG0m ¼ RTlnCMC ð3Þ where A(wt%) is the mass percentage of active ingredient, m1 (g) is the
weight of clean petri dish, m2 (g) is the weight of petri dish after dried.

2.3.5. HLB 2.3.9. Zeta potential and average particle size

The hydrophilic-lipophilic balance (HLB) values of three polymeric The 430 g/L tebuconazole SC sample was diluted 200-fold using de-
surfactants were measured via emulsification method [17]. First, a series ionized water. Zeta potential was measured by a Nano-ZS 90 particle
of standard oil samples with different HLB values (6, 8, 10, 12, 14, 16) size analyzer (Malvern, United Kingdom) and average particle size
were prepared with cottonseed oil (HLB = 6) and turpentine (HLB = was measured by a JL-1198 laser particle size analyzer (Chengdu Jingxin
16). Then 25 mL standard oil samples, 25 mL polymeric surfactant aque- Powder Analyzer Instruments Co. Ltd, China) at 25 °C.
ous solution (0.4 wt%) were added into the cylinder. After emulsified for
5 min using a FLUKO-FA25 high shear homogenizer, the mixture was 2.3.10. Viscosity
laid aside until the two phases were separated. The separation time of The viscosity of 430 g/L tebuconazole SC was tested using a NDJ-1 ro-
oil and water was recorded, and the HLB of the tested sample was con- tary viscometer (Shanghai Balance Instrument Factory).
sistent with the HLB of standard oil own the best emulsifying effect.
2.3.11. SEM measurement
2.3.6. Foam properties The morphologies of tebuconazole particles were analyzed by a
Foam property were tested as follows: 100 mL of 1 g/L polymeric Hitachi S-4800 instrument operating at 3.0 kV.
surfactant aqueous solution prepared by hard water with a hardness
of 342 mg/L was poured into a 250 mL cylinder with a stopper. Inverting 3. Results and discussions
the cylinder up and down for 30 times in 1 min. The foam volume at
0 min, 1 min and 15 min was recorded [7]. 3.1. Characterization of polymeric surfactants

2.3.7. Emulsification properties To elucidate the structural characteristics of three polymeric surfac-
The emulsion performance test was carried out as follows: 80 mL of tants, spectroscopic analyses, including FT-IR and 1H NMR, were
1 g/L polymeric surfactant aqueous solution and 20 mL of oil (toluene, performed (Fig. 1). As shown in Fig. 1a and b (FT-IR spectra), the inten-
liquid paraffin or o-dichlorobenzene) were added into a 100 mL beaker. sity of broad adsorption around 3450 cm−1 in SM-HEA and SM-HPA are
After emulsified for 5 min with a FLUKO-FA25 high shear homogenizer, higher because of the existence of extra hydroxyl comparable to SM-VS.

a SM-HEA b SM-HEA
c 3.78
SMHEA
SM-HPA 3.89 SMHPA
SM-HPA
SM-VS SMVS
SM-VS
4.2 4.0 3.8 3.6

-1
3450 cm 2980 cm-1 2920 cm
-1
1270 cm-1

1271 cm-1

1183 cm-1

4000 3000 2000 1000 4000 3500 3000 1000 8 6 4 2 0

Wave number (cm-1) Wave number (cm-1) f1 (ppm)

Fig. 1. FTIR spectra (a and b) and 1H NMR spectra (c) of SM-HEA, SM-HPA, and SM-VS.
4 S. Zhang et al. / Journal of Molecular Liquids 317 (2020) 114136

Additionally, the higher stretching vibration peaks of -CH2- and -CH3 at 75

2980 cm−1 and 2920 cm−1 in SM-HEA and SM-HPA attribute to the ad- SM-VS
ditional methyl and methylene in HEA and HPA (Fig. 1(a and b)). The 70 SM-HEA
characteristic peak at 1702 cm−1 is attributed to C_O in ester group,

Surface tension (mN/m)

SM-HPA
and the peaks around 1405 cm−1, 759 cm−1 and 701 cm−1 originate
from C\\H vibration of the benzene ring. The vibration peaks of C-O-C 65
in SM-HEA and SM-HPA are at 1270 cm−1 and 1271 cm−1, respectively
[11]. 616 cm−1 and 1183 cm−1 testify the existence of C\\S and -SO− 3
60
[18].
For 1H NMR spectrum (Fig. 1c), the signal around 7.2 ppm is ascribed
to phenyl protons in styrene. The peaks around 1.68 ppm are attributed 55
to the -CH2- and -CH- in the backbone. The peaks between 1.0 and 0.8
are related to the protons of methyl group [19]. For SMHEA and
SMHPA, the peaks at 3.78 ppm and 3.89 ppm are the chemical shift of 50
-CH2- connected to the ester group [20,21]. CMC
The Mn and Mw/Mn of three polymeric surfactants are listed in 45
Table 1. The Mn and Mw/Mn of SM-HEA, SM-HPA and SM-VS are 1964, 0 1 2 3
1720, 1807 and 2.52, 2.47, 2.79, respectively. The removal of small mol-
ecules by reprecipitation and dialysis resultes to the small dispersity.
Concentration (mmol/L)

Fig. 2. Surface tension of polymeric surfactant aqueous solution.

3.2. Surface activity

Table 2
Fig. 2 is the static surface tension curves of SM-HEA, SM-HPA and
The adsorption data of polymeric surfactants in aqueous solution at 25 °C.
SM-VS aqueous solution. The surface tension (γ) decreases initially
with the increase of the polymeric surfactant concentration and then Samples CMC γCMC Γmax Amin ΔG0m
(mmol/L) (mN/m) (×10−6 mol/m2) nm2/molecule (kJ/mol)
reaches a plateau zone. According to the break point and the plateau
zone of surface curves [22], the critical micelle concentration (CMC) SM-HEA 1.11 49.41 8.75 0.19 −16.85
and corresponding surface tension (γCMC) values of SM-HEA, SM-HPA SM-HPA 0.89 48.19 9.37 0.17 −17.40
SM-VS 1.46 53.21 7.30 0.23 −16.18
and SM-VS are evaluate to be 1.11 mmol/L, 0.89 mmol/L, 1.46 mmol/L
and 49.1 mN/m, 47.8 mN/m, 53.1mN/m, respectively. This indicates
that SM-VS has inferior surface activity compared to SM-HEA and SM-
HPA. This is probably because that -SO− 3 in SM-VS provides electrostatic
among all the polymeric surfactants. For polymeric surfactant, the ad-
repulsion, which leads to a lower density of surfactant molecules at the sorption of molecules at the interface is considered to be a diffusion-
interface [4]. Compared to SM-HEA, the more hydrophobic monomer controlled process at short times, with negligible desorption and no in-
HPA makes SM-HPA more hydrophobic, resulting its lower CMC and teraction between adsorbed and adsorbing macromolecules. Moreover,
γCMC [23]. In conclusion, SM-HPA has the best surface activity among the presence of higher hydrophilic or charged substituents can acceler-
the three polymeric surfactants. ate this adsorption process by increasing the area per molecule and pro-
The adsorption data of three polymeric surfactants are listed in ducing a lower cohesive force at the surface [25,26]. Therefore, SM-VS
Table 2. The smaller Γmax and larger Amin of SM-VS suggest the smaller exhibits the best foam producing ability and foam stability, and SM-
molecule packing density at the air-liquid interface [15]. Compared to HPA behaves conversely.
SM-HEA, SM-HPA has a lager Γmax and smaller Amin, this confers it supe-
rior surface activity. Meanwhile, the negative value of ΔG0m indicates the 3.4. Emulsion stabilization
micellization process is a thermodynamic spontaneous process. The
order of absolute value of ΔG0m is SM-HPA > SM-HEA > SM-VS, suggest- The hydrophile-lipophile balance (HLB) is a vitally important index
ing that SM-HPA molecule has the strongest driving force for micelliza- to measure the performance of surfactant quantitatively in application
tion or adsorption at the air-liquid interface [22]. This may be because
that the greater hydrophobic interaction of SM-HPA could lead to an
easier formation of micelles [4]. 120
0 min
3.3. Foam properties 1 min
15 min
Volume of foam (mL)

The investigation between the polymeric surfactant structure and

foam properties is very important for its application in pesticide formu- 80
lation where foam is generally not welcome for its negative impact in
the production and spray [24]. As shown in Fig. 3, about 69%, 71% and
61% foam collapse after 15 min for SM-HEA, SM-HPA and SM-VS, sug-
gesting that SM-VS is the best foaming agent and foam stabilizer
40
Table 1
Molecular weights of three polymeric surfactants.

Sample Monomer ratio (mol) Mn Mw/Mn

St MAA HEA HPA VS

0
SM-HEA 1 4 1 1964 2.52 SM-HEA SM-HPA SM-VS
SM-HPA 1 4 1 1720 2.47
SM-VS 1 4 1 1807 2.79
Fig. 3. The foaming and foam stability of SM-HEA, SM-HPA, and SM-VS.
 S. Zhang et al. / Journal of Molecular Liquids 317 (2020) 114136 5

in pesticide formulation [27]. Table 3 presents the HLB value of 1200

polymeric surfactants and the separation time of the prepared O/W SM-HEA
emulsion. The longer the separation time, the better the stability of SM-HPA
the O/W emulsions. Typically, surfactant with HLB values in the range 1000 SM-VS
from 3 to 6 can stabilize W/O emulsions, whereas those with HLB values

Viscosity (mPa.S)
in the range from 8 to 18 stabilize O/W emulsions [28]. The HLB values
of SM-HEA, SM-HPA, and SM-VS are 11.4, 11.0 and 15.8, indicating that
they can be used to stabilize O/W emulsion. According to Table 3, it can 800
be concluded that the larger the HLB value of polymeric dispersant, the
better the stability of the O/W emulsions. This is consistent with
Tadros's findings [8]. The phase separation time of O/W emulsions pre-
600
pared by three polymeric dispersants with liquid paraffin are 743 s,
608 s, 1114s, longer than the separation time of emulsions prepared
by toluene, although both oils have almost the same density. It is re-
ported that the interfacial tension at an oil–water interface decreases 400
with the increase of the polarity of oil molecules, which would be ex-
0 2 4 6 8
pected to cause coalescence and Ostwald ripening [29,30]. Therefore,
the O/W emulsion prepared by liquid paraffin is more stable because Dosage of dispersant (wt%)
of its lower polarity comparable to toluene. Furthermore, the difference
in density of oil and water could influence the stability of O/W emulsion. Fig. 4. Effect of the dosage of SM-HEA, SM-HPA, and SM-VS on the viscosity of 430 g/L
This can be verified by the longer time (265 s, 181 s, 500 s) of the phase tebuconazole SC.

separation from the emulsion prepared by toluene with SM-HEA, SM-

HPA, SM-VS in comparison to the time (138 s, 113 s, 396 s) of phase sep- SC. The zeta potential of tebuconazole particles in SC without disper-
aration from emulsions prepared by o-dichlorobenzene. According to sants is approximately −22 mV, indicating that the tebuconazole parti-
the Stokes equation, small density difference between oil and water cle is negatively charged. When the amount of the polymeric surfactant
can reduce the extent of creaming and coalescence of oil droplets in increases from 0 to 4 wt%, zeta potential of tebuconazole particle in all
water [31]. Therefore, the emulsions prepared by toluene exhibit more SCs decreases rapidly. At the concentration of 4 wt%, the absolute
stable because of its smaller density difference with water comparable value of zeta potential reaches the maximum, suggesting the saturated
to the difference between o-dichlorobenzene and water. adsorption of surfactant. It is noteworthy that the zeta potential increase
conversely again when the dosage of surfactants exceeds 4 wt%. This
3.5. Influence of polymeric surfactants on 430 g/L tebuconazole SC may be because that excessive counter ions of surfactants enter into
the diffusion layer of the double electrical layer [32]. Therefore, the
3.5.1. Viscosity of 430 g/L tebuconazole SC zeta potential increased conversely again. Moreover, the absolute
The dispersive performance of the dispersant is crucial to improve value of zeta potential of 430 g/L tebuconazole SC prepared by SM-VS
the SC's stability and can be reflected in the viscosity of the suspension is largest, indicating that SM-VS could provide stronger electrostatic re-
system. As depicted in Fig. 4, plotting the viscosity vs dosage of disper- pulsion than SM-HEA and SM-HPA.
sant, the viscosity of 430 g/L tebuconazole SC decreases rapidly when
the dispersant amounts increase from 1 wt% to 4 wt%. At the dosage of 3.5.3. Stabilization of 430 g/L tebuconazole SC vs thermal storage
4 wt%, the viscosity of formulations prepared by all three polymeric sur- The changes of suspension rate and particle size distribution are im-
factants reaches a minimum, indicating saturated adsorption. After the portant quality indexes and often used to character the physical stability
dosage exceeds this critical value, the viscosity begins to increase con- of SC [3,33]. Compared to the samples without dispersant, the suspen-
versely. When the amount of dispersant added is too low, resulting in sion rate (Table 4) of 430 g/L tebuconazole SC prepared by SMHEA,
a very low dispersant molecules coating on the pesticide particles, insuf- SMHPA, and SMVS are significantly improved. After 14 days of thermal
ficient repulsion between the particles could not prevent their aggrega- storage, the suspension rate of SCs prepared by SM-HPA is still greater
tion. Whereas after achieved the saturated adsorption, the excess
dispersant molecules arrange in opposite direction and destroy the
-20 SM-HEA
best steric hindrance and electrostatic repulsion between pesticide par-
ticles [32]. Therefore, the viscosity increases conversely again. Among all SM-HPA
the studied polymeric surfactants, the viscosity of 430 g/L tebuconazole SM-VS
SC prepared by SM-HPA is the lowest at the same amount, indicating -30
Zeta potential (mV)

SM-HPA behaves better than others.

3.5.2. Zeta potential of 430 g/L tebuconazole SC -40

According to the DLVO theory, zeta potential is a measure of the net
charge on a colloidal particle and could character the electrostatic repul-
sion between pesticide particles [32]. Fig. 5 depicts the effect of three
polymeric surfactants on the zeta potential of 430 g/L tebuconazole -50

Table 3
Emulsifying power of SM-HEA, SM-HPA, and SM-VS. -60
Samples HLB Time for separation (s)
0 2 4 6 8
Liquid paraffin Toluene O-dichlorobenzene
Dosage of dispersant (wt%)
SM-HEA 11.4 743 265 138
SM-HPA 11.0 608 181 113
Fig. 5. Effect of polymeric surfactant dosage on the zeta potential of 430 g/L tebuconazole
SM-VS 15.8 1114 500 396
SC.
6 S. Zhang et al. / Journal of Molecular Liquids 317 (2020) 114136

Table 4 size [34]. Herein, aggregation is a dominant factor resulting the increase
Stability of 430 g/L tebuconazole SC vs thermal storage. of tebuconazole particle size of SC prepared by SM-HEA, while Ostwald
Samples Suspension rate (%) Particle size (D90, μm) ripening plays a key role in the growth of tebuconazole particle dis-
1st 14th day after thermal 1st 14th day after thermal
persed by SM-VS [34,35].
day storage day storage
3.5.4. Adsorption mechanism of polymeric surfactants for tebuconazole
None 47.78 15.12 15.07 32.25
SM-HEA 97.21 93.04 3.56 5.52 particle
SM-HPA 99.52 97.05 3.25 4.12 As the pesticide particle size decreases after milling, the specific sur-
SM-VS 94.52 89.56 8.79 13.21 face area and surface energy increase significantly, resulting the parti-
cles re-aggregating spontaneously [36]. Polymeric surfactant could
decrease the surface energy and improve the stabilization of particles
than 97%. The change of tebuconazole particle size is minimal among all by binding to multiple surface sites at the same time and forming a du-
the SCs. Moreover, the persistent foam is also minimal, which is consis- rable adsorption layer on the surface of particles [4]. The adsorption
tent with the results of foam experiments. This result indicates that SM- mechanism that describes the type of contact between the polymer
HPA poses greater potential application in 430 g/L tebuconazole SC than and the solid surface can be broadly classified into two categories, phys-
others. ical adsorption and chemical adsorption [1]. Physical adsorption is a
The particle size has a significant impact on the viscosity and stabil- weak interaction while chemical adsorption refers a strong interaction.
ity of SC. Thus, the changes of the particle size of 430 g/L tebuconazole Other types of interaction include hydrogen bonding and hydrophobic
SCs before and after thermal storage is investigated (Table 4). The parti- interaction. Which adsorption mechanism act the predominance role
cle size (D90) of 430 g/L tebuconazole SC prepared by SM-HPA increases depends on the specific conditions of the polymeric dispersants and
from 3.25 to 4.12 μm after 14 days thermal storage, less than the particle particle surface. Attractive electrostatic forces involve charged surfaces
size increase of other SCs, indicating that SM-HPA can effectively inhibit attracting and accumulating oppositely charged ions while repulsive
crystal growth of tebuconazole particles vs the thermal storage process. electrostatic forces exist between anionic molecules such as
This can be verified by the results of FESEM images of tebuconazole par- polycarboxylate and negatively charged particles. If the attractive forces
ticles (Fig. 6c and d). Although no obvious agglomeration occurs among such as hydrogen bonding exceed the electrostatic repulsive forces, the
the SCs prepared by SM-HEA and SM-VS, the particle size still increases adsorption of an anionic polymer onto a negatively charged surface may
obviously after thermal storage. Note that the particle size of SCs pre- occur [1]. In this study, the adsorption of the polymeric surfactants on
pared by SM-HEA and SM-VS changes in different way. For SM-HEA, the surface of tebuconazole particles improve the stabilization of
particle aggregation occurs after thermal storage. Regarding SM-VS, 430 g/L tebuconazole SC by providing electrostatic repulsion. The nega-
particle aggregation already exists before thermal storage. And the tive sulfonate group of SM-VS increases the repulsive electrostatic force
large particles grow at the expense of small particles after thermal stor- between SM-VS and negatively charged tebuconazole particles, hinder-
age. Moreover, the surface of tebuconazole particle become smoother in ing the adsorption of the surfactant molecules on the surface of the
all SC samples, indicating that Ostwald ripening occurs in all of them tebuconazole particles. While for SM-HEA and SM-HPA, the exist of
after thermal storage. Actually, aggregation and Ostwald ripening -OH in HEA and HPA increase the adsorption affinity between surfactant
could occur simultaneously and lead to the increase of pesticide particle molecules and the pesticide surface, thus increasing the surfactant

a b c

50μm 50μm 50μm

d e f

50μm 50μm 50μm

Fig. 6. FESEM imagines of tebuconazole particles before(left) and after(right) thermal storage with different surfactant SM-HEA (a and b), SM-HPA (c and d) and SM-VS (e and f).
 S. Zhang et al. / Journal of Molecular Liquids 317 (2020) 114136 7

OH
Adsorption/Dispersion

Pesticide particle Surfactant

Hydrogen bond Electrical double layer

Fig. 7. Schematic diagram of adsorption mechanism of SM-HEA, SM-HPA and SM-VS on pesticide particles.

adsorption density on the surface of tebuconazole particles. Moreover, activity and performance in improving the stability of pesticide formu-
additional hydrophobic interaction by methyl in HPA confers SM-HPA lation is influenced by the nature and structure of the hydrophilic
stronger adsorption affinity onto the tebuconazole particles and im- segment.
proves their stability by modifying particle-particle interactions [37].
Therefore, SM-HPA performs best in improving the stability of 430 g/L CRediT authorship contribution statement
tebuconazole SC, although the absolute value of zeta potential of formu-
lation is lower than the absolute values of other formulations. In conclu- Shupeng Zhang: Conceptualization, Methodology, Formal analysis,
sion, these results from zeta potential, viscosity, suspension rate and Writing - original draft. Xiaodong Yang: Validation. Zhenbei Tu: Inves-
particle size experiments suggest that SM-HPA performs best in im- tigation. Wendong Hua: Investigation, Resources. Penghui He: Data
proving the physical stability of the 430 g/L tebuconazole suspension curation. Haihui Li: Resources. Bo Zhang: Writing - review & editing,
concentrate by both electrostatic and steric stabilization. The steric sta- Project administration. Tianrui Ren: Visualization, Supervision.
bilization plays a dominant role (Fig. 7).

4. Conclusion Declaration of competing interest

Three random polymeric surfactants were synthesized via copoly- We declare that we have no financial and personal relationships
merization of styrene and methacrylic acid with three different mono- with other people or organizations that can inappropriately influence
mers (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and vinyl our work, there is no professional or other personal interest of any na-
sulfonate, sodium salt) and denoted as SM-HEA, SM-HPA and SM-VS, ture or kind in any product, service and/or company that could be con-
respectively. Their structure was confirmed by FTIR and 1H NMR spec- strued as influencing the position presented in, or the review of, the
tra. The measurement of surface tension shows that SM-HPA possesses manuscript entitled.
higher surface activity than SM-HEA and SM-VS. The adsorption data
evaluated using Mn shows that SM-VS has a lower Γmax of Acknowledgements
7.30 × 10−6 mol/m2 in comparison to SM-HEA (8.75 × 10−6 mol/m2)
and SM-HPA (9.37 × 10−6 mol/m2). Moreover, SM-VS exhibits higher This work was supported by the Chinese Characters of Shanghai Ag-
foamability and emulsifying properties for O/W emulsion than SM- ricultural Sciences (2018) No. 3-3.
HEA and SM-HPA. By using as dispersant in 430 g/L tebuconazole SC,
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