Received: 29 June 2017

| Accepted: 2 December 2017

DOI: 10.1002/adv.21931

RESEARCH ARTICLE

Synthesis of polycarboxylate superplasticizers using an acrylic

acid-­rich wastewater from acrolein production

Jikai Pei1,2 | Ziwei Wang1,2 | Jianguo Ren1,2 | Diansheng Liu1,2

1
Concrete Admixtures Technology Research
Center, Shanxi University, Taiyuan, China
Abstract
2
College of Chemistry and Chemical In this paper, an acrylic acid-­rich wastewater from the production of propylene to
Engineering, Shanxi University, Taiyuan, acrolein was used to synthesize the polycarboxylate superplasticizers. First, the
China acrylic acid-­rich wastewater was oxidized. Then, two kinds of unsaturated polyether
Correspondence macromonomers {methallyl polyethylene glycol (HPEG) and isoprenol polyethyl-
Diansheng Liu, Concrete Admixtures ene glycol (IPEG)} and the oxidized wastewater were copolymerized with it, respec-
Technology Research Center, Shanxi
tively, by free radical polymerization in aqueous solution. The monomer conversion,
University, Taiyuan, China.
Email: [email protected] molecular weight, molecular weight distribution of the copolymers of gel permeation
chromatography (GPC) were characterized. The performance of the two copolymers
was characterized by measuring paste flow, adsorption using GPC method, and the
applied behavior of premixed concrete. The results showed that the synthesized co-
polymers could meet the requirement of application in contrast to the commodity
product.

KEYWORDS
acrylic acid-rich wastewater, adsorption, copolymer, macromonomers, polycarboxylate superplasticizer

1 | IN T RO D U C T ION reported.[4] Some researchers attempted to recycle the acrylic

acid by a chemical reaction, but it is difficult for the time
Acrolein is a very important organic synthetic material, being.[5] Acrylic acid is an important organic synthetic ma-
which is mainly used to synthesize the methionine as animal terial and monomer. Therefore, acrylic acid in wastewater
feed additives. There are many methods for the production of should be reused. The acrylic acid-­rich wastewater can be di-
acrolein. Now, about 80% of acrolein has been produced by rectly polymerized. However, because of the impurities, this
the oxidation of propylene. However, plenty of acrylic acid-­ kind of polyacrylic acids cannot be widely used. Based on
rich wastewater was generated by this procedure.[1–3] There these reasons, in this research, we tried to use the wastewa-
are two kinds of approaches for this kind of wastewater in- ter directly. The acrylic acid-­rich wastewater and unsaturated
cluding incineration and recycling. Recycling the wastewa- polyether macromonomers were copolymerized as polycar-
ter is better than burning it. The treatment of incineration boxylate superplasticizers in this work. Most of the polycar-
is expensive and generates a second air pollution. There are boxylate superplasticizers are synthesized from pure acrylic
three methods of recycling the wastewater including rectifi- acid monomer and deionized water as solvent,[6] but here, the
cation, the osmotic membrane separation, and chemical sep- acrylic acid-­rich wastewater was used as the monomer and
aration. The rectification method is fit for the factories that the solvent for the preparation of a special polycarboxylate.
have also produced the acrylic acid and acrylic ester, mean- Polycarboxylate superplasticizer is a kind of comb-­like poly-
while, the cost of rectification is very high. The method of mer surfactant and also a polyelectrolyte.[7,8] It consists of
osmotic membrane separation is just feasible in laboratory. adsorption groups and long side chains.[9] Polycarboxylate
So far, the industrial application of membranes for separat- superplasticizers adsorb on the dispersed substances by the
ing the wastewater of acrolein production has not yet been anchoring groups based on electrostatic repulsion and steric

Adv Polym Technol. 2017;1–7. wileyonlinelibrary.com/journal/adv © 2017 Wiley Periodicals, Inc. | 1

2
|    PEI et al.

2 | EXPERIM ENTAL
2.1 | Materials
Acrylic acid-­rich wastewater of producing acrolein was sup-
plied by Chongqing Ziguang Chemicals, China. The ingredi-
ents see Table 1. Methallyl polyethylene glycol (HPEG2400,
2,400 g/mol) and isoprenol polyethylene glycol (IPEG2400,
2,400 g/mol) were supplied by Liaoning Oxiranchem
Inc., China. Hydrogen peroxide (H2O2, 30 wt.%) was pur-
chased from Sinopharm, China. L-­ Ascorbic acid (VC),
2-­Methyl-­2-­propene-­1-­sulfonic acid sodium salt (MAS) and
sodium hydroxide (NaOH) were all purchased from Shanghai
Aladdin, China. All other reagents were analytical grade. The
FIGURE 1 The structural formula of HPEG2400 and IPEG2400 cement (P·I 42.5) used in this research was supplied by China
United Qufu, China. Its chemical composition and physical
hindrance.[10–13] Lots of research results indicated that the properties are presented in Table 2. HS-­109 polycarboxylate
steric hindrance effect is the main action mechanism.[14,15] superplasticizer (goods; Shanda Hesheng, Taiyuan, China)
The backbone and side chain can be adjusted to get the ef- and HW-­1 polycarboxylate superplasticizer (goods, Nippon
fects needed.[16–20] Polycarboxylate superplasticizer is also a Shokubai, Japan) were used for comparison (Table 4).
type of hydrophilic polymer surfactant which has both an-
ionic and nonionic structures. So, the surface activity of this
2.2 | Synthesis of the polycarboxylate
copolymer, such as HLB (hydrophile–lipophile balance),
superplasticizers
foamability, must be considered in real researches and appli-
cations.[21–23] The function of nonadsorbing polymer in the • Pretreatment: Because of the traces of acrolein in this
cement disperse system maintains the balanced state.[24,25] wastewater, a certain quantity of H2O2 was added into the
In this paper, we used the treated acrylic acid-­rich wastewa- acrylic acid-rich wastewater mixing for 4–6 hr in ambient
ter and two kinds of unsaturated macromonomers methallyl temperature. Then, the nitrogen was bubbled in it for 1 hr.
polyethylene glycol (HPEG) and isoprenol polyethylene gly- Store in a cool place.
col (IPEG) (Figure 1) for copolymerization. The applicability • Polymerization: HPEG2400 (or IPEG2400) 180 g, MAS
of these two synthesized polycarboxylate superplasticizers 2 g, and the acrylic acid-rich wastewater 180 g were poured
has been investigated. The dispersing effect was tested utiliz- into a 1,000 ml four-neck flask. The solid materials were
ing a “mini slump test” and high flowing pumped concrete. dissolved by increasing the temperature and stirring. The
The copolymers were characterized by gel permeation chro- oxidizer H2O2 6 g was added in the flask when the tem-
matography (GPC). We characterized the interaction between perature is heated to 60°C. Meanwhile, A solution (VC
the superplasticizers and the cement particles by the adsorp- 1.9 g dissolving in 50 g deionized water) was dropped.
tion testing. The mechanical properties of the copolymers in 10 min later, another solution B (acrylic acid-rich waste-
the premixed concrete were also tested. The polycarboxylate water 150 g) was also dropped. The dropping time must be
superplasticizers synthesized in this research can meet the controlled that A solution completed in 3 hr and B solu-
demand of application in contrast to the commodities. tion completed in 2.5 hr. The temperature is controlled in

TABLE 1 Ingredients for the

Component Acrylic acid (AA) Acetic acid Hydroquinone Rest
wastewater of producing acrolein
Mass percent (%) 4.5–7.0 0.2–0.3 0.1–0.2 <0.1

TABLE 2 Chemical composition and physical properties of cement

Physical properties

Blain
specific 80 μm Soundness
surface screening of cement
Cement CaO SiO2 Fe2O3 Al2O3 MgO SO3 f-­CaO Loss (m2/kg) residue (%) (mm)
Content (%) 62.59 20.6 3.23 4.61 2.61 2.92 0.75 2.04 353 2.5 0.5
PEI et al.   
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TABLE 3 Molar compositions of the

Amounts of raw materials
synthesized polycarboxylate
superplasticizers Acrylic
Molar ratio AA/ acid-­rich
HPEG2400 wastewater HPEG2400/
Copolymers (IPEG2400)/MAS (g) IPEG2400 (g) MAS (g)
a
P-­HPEG2400 2.8–4.3 /1/0.2 330 180 2
a
P-­IPEG2400 2.8–4.3 /1/0.2 330 180 2
a
The concentration of acrylic acid-­rich wastewater is minimum 4.5% and maximum 7%.

TABLE 4 The physical indexes of

Solid content
four kinds of polycarboxylate
Sample Appearance (%) Density (g/cm3) pH
superplasticizers
HS-­109 Pale yellow viscous 39.6 1.083 6.8
liquid
HW-­1 Pale yellow viscous 40.1 1.085 7.2
liquid
P-­HPEG2400 Yellow viscous 35.2 1.074 7.7
liquid
P-­IPEG2400 Yellow viscous 35.0 1.073 7.5
liquid

60 ± 2°C. After the dropping completed, it is necessary to GPC. Then, the adsorption ratio in the cement particles of
maintain the temperature and stirring for 1 hr. When the the copolymers was calculated according to these two con-
reaction completed, a NaOH solution (NaOH 13 g dissolv- centrations. The measurements were carried out at 0.15% (by
ing in 30 g deionized water) was added into the polymer weight of cement) dosage.
solution for neutralization. The final product is a yellow
transparent viscous liquid and is marked as P-HPEG2400
(or P-IPEG2400). In Table 3, the exact amounts of mono-
2.3.3 | Cement paste flow
mers and the molar composition of synthesized copolymers The testing of cement paste flow is according to GB/T 8077-­
are shown. 2012: methods for testing uniformity of concrete admixture.
The cement 300 g, water 87 g, and 0.15% superplasticizers
(by weight of cement) are mixed in cement paste mixer. The
fluidity of cement paste is measured using the mini slum flow
2.3 | Characterization and performance
cone in 5, 20, 40, 60, and 80 min.
2.3.1 | Gel permeation chromatography
2.3.4 | Concrete workability and
Waters 1515 pump, column box, and Waters 2414 RI detector
compressive strength
consist of the GPC system (Waters 1515; Waters, America).
We use one Ultrahydrogel 250 and two Ultrahydrogel 120 The concrete workability is one of the most important indexes
connecting in series columns. The liquid phase is 0.1 mol/L for premixed concrete. We tested the performance of the co-
sodium nitrate. The test samples were dissolved in liquid polymers according to GB 8076-­2008: concrete admixtures.
phase. Polymer molecule weight, molecule weight distribu- The compressive strength of hardened concrete was meas-
tion, and conversion were tested. ured after 3, 7, and 28 days of standard curing according to
GB/T 50081-­2002: standard for test method of mechanical
properties on ordinary fresh concrete.
2.3.2 | The adsorption of the two
synthesized copolymers in cement paste
The cement paste (W/C = 3.0, water/cement) is prepared in
3 | RESULTS AND DISCUSSIO N
adsorption testing. The synthesized copolymers were tested
for their adsorption onto cement using the GPC method.
3.1 | Characterization of the two copolymers
First, the superplasticizers concentrations before adsorp- The two synthesized copolymers solutions and two com-
tion and after mixing with cement for 5 min were tested by modities solutions were compared regarding their solids
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|    PEI et al.

FIGURE 2 Gel permeation chromatography chromatogram of P-­HPEG2400 polymer

TABLE 5 Molar masses and polydispersities (PDIs) of the two TABLE 6 Adsorption ratios of the two synthesized copolymers
synthesized copolymers
Adsorbed
PDI amount (mg
Copolymers Mw (g/mol) Mn (g/mol) (Mw/Mn) solution/g Adsorption
Superplasticizers Dosage (%) cement) ratio (%)
P-­HPEG2400 41,335 22,635 1.83
P-­IPEG2400 39,249 20,394 1.92 P-­HPEG2400 0.15 0.98 65
P-­IPEG2400 0.15 0.81 54

content, pH, density, and appearance (Table 4). In Figures 2

and 3, it can be seen that copolymers molecules with higher technique, we can conclude that P-­ HPEG2400 has more
molecular weight elute earlier from the chromatography effective absorptive groups in initial phase, which brings
column. The copolymerization conversion was obtained more strong absorptive power. P-­IPEG2400 has less effec-
by quantitative testing of GPC. The copolymerization con- tive absorptive groups in initial phase than P-­HPEG2400.
version of P-­HPEG2400 is 77.98% and of P-­IPEG2400 is The adsorption ratio of P-­IPEG2400 is much lower than of
80.75%. It can be seen that P-­HPEG2400 had more unre- P-­HPEG2400, confirmed that P-­IPEG2400 should provide
acted monomers than P-­IPEG2400 from chromatograms. better slump retention properties than P-­HPEG2400 because
The two copolymers have narrow polymer distribution of nonadsorbing polymers.[24]
(P-­HPEG2400: PDI = 1.83 and P-­IPEG2400: PDI = 1.92)
under the synthesis conditions. The polycarboxylate su-
3.3 | The fluidity of cement paste
perplasticizers using wastewater had good copolymeriza-
with the copolymers
tion conversion and narrow molecule weight distribution
(Table 5). The cement paste flow of P-­HPEG2400, P-­IPEG2400, HS-­
109 and HW-­1 over a period of 80 min was tested (Figure 4).
The initial fluidity of P-­HPEG2400 is the biggest in all of the
3.2 | Adsorption
samples probably because of more effective adsorption groups
We tested the adsorption ratio after cements were mixed and small molecules (such as acetic acid, propionic acid) in
with the copolymers for 5 min. The adsorption ratio of P-­ the acrylic acid-­rich wastewater which possess dispersion ef-
HPEG2400 is 65% and P-­ IPEG2400 is 54% (Table 6). fect, but the 80 min fluidity of P-­HPEG2400 is the smallest
Because of the same molar ratio and the same polymerization in all of the samples probably because of strong adsorption
PEI et al.   
| 5

FIGURE 3 Gel permeation chromatography chromatogram of P-­IPEG2400 polymer

TABLE 7 The mix proportion of concrete

Mineral
Cement (C) Fly ash (FA) powder (MP) Sand (S) Aggregate (G) Water (W) PCEs
3
Dosage (kg/m ) 210 84 125 846 955 180 1.8
PCEs, polycarboxylate superplasticizers.

ability and less no-­adsorbing copolymers in the pore solution. TABLE 8 The workability results of pumped concrete with the
P-­IPEG2400 provides better slump retention in contrast to copolymers
the P-­HPEG2400, even to HW-­1. The performance of HW-­1
Initial slump/ 1 hr slump/ Air content
is the best in all of polymers. The fluidity and fluidity reten-
Sample flow (mm) flow (mm) (%)
tion of HS-­109 is average performance during 80 min. The
cement paste dispersion of these two synthesized copolymers Blank 200/550 160/400 1.8
is good compared with the two commodities. HS-­109 200/600 180/550 3.4
HW-­1 220/620 215/600 4.5
P-­HPEG2400 225/625 180/550 2.8
3.4 | Concrete workability and
compressive strength P-­IPEG2400 200/590 205/580 4.0

To measure the application performance of these two co-

polymers, we chose a local ready mixed concrete plant to concrete slump loss is small after 1 hr. So, we can get the
prepare the pumped concrete. The concrete mix propor- conclusion that the concrete workability with these two co-
tion can be found in Table 7. The sand percentage is 45% polymers meets the demands of ready mixed concrete.
and water/binder is 0.45. The results were seen in Table 8. The concrete compressive strength of these four samples
We observed that the concrete using these two copolymers was tested. The results were shown in Figure 5. The early
have good workability with no segregation and no bleed- compressive strength of P-­HPEG2400 increased a lot com-
ing in the test. The mixed concretes are not sticking and pared to the blank but increased slower after 28 days. The
not heavy. The prepared concrete can be easily pumped. compressive strength of P-­ IPEG2400 increased higher in
Meanwhile, the air content of the concrete is all less than 28 days than P-­HPEG2400. HW-­1 had better performance
6% that meet the GB 8076-­2008: concrete admixtures. The during the entire curing period than HS-­109. It is possible
6
|    PEI et al.

to prepare high-­performance concrete for P-­HPEG2400 and

P-­IPEG2400. From the compressive strength, we can find
that the concrete with P-­IPEG2400 has higher denser than
P-­HPEG2400.

3.5 | Calculation of molecular

structure for the starting materials of
HPEG2400 and IPEG2400
To understand the differences between P-­ HPEG2400
and P-­IPEG2400, we calculated the dipole moments and
charges of the two starting materials which were used for
synthesizing HPEG2400 and IPEG2400, respectively,
methallyl alcohol and isoprenol. In Figure 6, we can see
that the dipole moment direction of methallyl alcohol is
FIGURE 4 Cement paste flow curves of the four copolymers away from the double bond, but the dipole moment direc-
tion of isoprenol is pointing to the double bond. It shows
that the double bond of isoprenol have higher polymeriza-
tion activity than methallyl alcohol. The absolute value
of charge of isoprenol is bigger than methallyl alcohol.
So, we concluded that IPEG2400 showed higher copo-
lymerization activity with acrylic acid than HPEG2400.
According to the former work of our research team, the
testing reactivity ratio of acrylic acid and IPEG2400 are
rAA = 1.131 and rIPEG = 0.042.[26] The testing reactivity
ratio of acrylic acid and HPEG2400 is rAA = 1.54 and
rHPEG = 0.[27] It indicated that P-­IPEG2400 is close to the
ideal copolymerization. P-­IPEG2400 has more homoge-
neous structure than P-­HPEG2400. The more homoge-
neous structural properties can lead to better retention
performance in cement mortar and concrete. The theo-
retic prediction and the results of experiment had some
FIGURE 5 Concrete compressive strength of the four correlation.
copolymers

F I G U R E 6 The dipole moment

and charges of the starting materials of
HPEG2400 and IPEG2400
PEI et al.   
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