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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

Synthesis of the VPEG Polycarboxylate Superplasticizer with

Controllable Activity and Its Properties

Wenhong Chen1, Lei Deng2, Yu Jiang3 and Jianmei Li4

1
KZJ New Materials Group Guizhou Co., Ltd. Longli, Guizhou, China
2
KZJ New Materials Group Guizhou Co., Ltd. Longli, Guizhou, China
3
KZJ New Materials Group Guizhou Co., Ltd. Longli, Guizhou, China
4
KZJ New Materials Group Guizhou Co., Ltd. Longli, Guizhou, China
Corresponding author’s e-mail：[email protected]

Abstract. This paper focuses on the synthesis of a kind of VPEG polycarboxylate

superplasticizer with controllable activity with 4-hydroxybutyl vinyl polyoxyethylene ether
(VPEG), acrylic acid (AA) and fumaric acid (FMA) as the main raw materials. Through the
experimental results, it can be found that the optimum process conditions are as follows: the
water-reducing admixture has ideal fluidity and workability in concrete, with the temperature
of 20℃, the reaction system concentration of 40%, the mass ratio of acid to ether of 9.2%, and
the initiator and the chain-transfer agent respectively accounting 0.3% and 0.09% of the total
mass.

1.Introduction
With the advancement of admixtures and concrete industries, buildings such as skyscrapers, grand
bridges and long tunnels are frequently constructed, which call for the concrete with high performance
and high strength. But in the process of mixing construction, the concrete with high performance and
high strength often encounter problems such as partial viscosity, poor flow performance, excessive
slump loss, amplification, segregation, and poor sensitivity [1]. These problems are all related to the
poor gradation of sand and gravel, large mud content, and poor-quality admixtures. The effect of
polycarboxylate superplasticizer on the performance of concrete cannot be ignored. Because of its
mature production technology, relatively simple production process, economic applicability,
diversified and controllable molecular structure, and the concrete with the advantages of high-water
reduction rate under the condition of low parameters, polycarboxylate superplasticizer has become one
of the indispensable admixtures in the market.
Polycarboxylate superplasticizer is mainly prepared by the reaction of polyether macromonomer
with the acrylic acid containing hydrophilic group in unsaturated double bonds and its derivatives. It
has superior water-reduction rate, long slump protection, good dispersion to cement [2], and obvious
improvement on the concrete workability and compressive strength. Its molecular structure mainly
contains carboxyl, hydroxyl, amino, sulfonic acid and other functional groups[3].
Due to the poor gradation of sand and gravel materials, large mud content and the introduction of
inferior admixtures, and unqualified site operation of polycarboxylate superplasticizer, it is necessary
to modify it, so as to ensure its performance can meet requirements of site operation. As a kind of
vinyl-terminated polyether macromonomer with high reactivity, VPEG is mainly prepared by
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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

ethoxylation with 4-hydroxybutyl vinyl ether as the starting agent [4]. In order to solve the quality
problems caused by the difficulty of concrete construction and poor workability, in this paper,
4-hydroxybutyl vinyl polyoxyethylene ether (VPEG), acrylic acid (AA) and fumaric acid (FMA) are
used to do reaction experiment, so as to overcome difficulties in concrete construction and solve the
problems of poor workability [5].

2. Experiment

2.1. Raw Materials and Equipment

The details of raw materials used in this experiment are shown in Table 1:
Table 1 raw materials
Raw materials Specifications Factory
4-hydroxybutyl vinyl Molecular Lin 'an Technology
polyoxyethylene ether
weight：3000 chemical Co.,Ltd.
VPEG
Acrylic acid Main content： Fujian Binhai Chemical
AA ≥99.5% Industry Co.,Ltd.
Mumaric acid Main content： China Bluestar Harbin
FMA ≥99.0% Petrochemical Co.,Ltd.
Synthetic Methylallyl sulfonate Main content： Jinan Blueprints
raw TGA ≥99.0% Chemical Co.,Ltd.
materials Hydrogen peroxide Guiyang Nanming
Main content：
solution Hongfeng Chemical
H2O2 ≥27.5 % Co.,Ltd.
Ascorbic acid Main content： Sichuan Lingde Chemical
Vc ≥99.5% Co.,Ltd.
Guiyang Nanming
Sodium hydroxide Solid content：
Hongfeng Chemical
NaOH 30% Co.,Ltd.
Water of
Cement standard Guizhou Hongshi Cement
C consistency： Co.,Ltd.
26.2%
Fineness Zhongjiao Road and
Mechanism of green
modulus Bridge North China
sand
:2.6-3.4 Engineering Co.,Ltd.
Performance Zhongjiao Road and
Gravel Particle
test Bridge North China
G1 size:5-10mm
raw Engineering Co.,Ltd.
materials Zhongjiao Road and
Gravel Particle
Bridge North China
G2 size:10-20mm
Engineering Co.,Ltd.
Water
Water supply Made by oneself
W
Common
polycarboxylic acid Solid content： KZJ New Materials
water reducer 40% Group Guizhou Co., Ltd.
PC
The details of the main instruments used in this experiment are shown in Table 2:

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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

Table 2 main instruments

laboratory apparatus Type Main technical parameters
Water bath DFY-5L/30℃ Capacity:5000ml
Electric mixer JJ-1 Rotary speed:3000r/min
Peristaltic pump BT100-01 Rotary speed:0.1～100 rpm
Automatic control of program
Cement mixer NJ-160B
time:255±3s
Single horizontal shaft
HJW-60 Quota mixing quantity:60L
test mixer
Digital pressure testing
DYE-2000 Maximum load:2000KN
machine
Gel permeation
2414 Moving phase:0.1mol/LNaNO3 liquor
chromatograph
Infrared
spectrometernfrared FTIR-850 KBr The chip daub
spectrometer

2.2. Synthesis Method

First, weigh a certain amount of VPEG and FMA into a four-port flask with a stirrer. Then add
appropriate amount of W, turn on the stirrer, set the temperature (-10 ~ 30℃), and drop the solutions
of A, B and C. The three solutions are respectively composed of H2O2 and W, AA and W, and TGA,
Vc and W. When the dropping reaction of A for 2h, the dropping reaction of B and C for 2h and
constant temperature reaction for 1h, then adding 2% NaOH and stirring for 5 min, a light yellow and
transparent functional controllable polycarboxylate superplasticizer (PEFA) with the solid content of
40% can be obtained.

2.3. Performance Test Methods

(1) Fluidity of cement paste: the water cement ratio is 0.29, and the solid content of admixture is 0.23%
by using Hong Shi P.O42.5 cement according to GB/T 8077-2012 Test Method for Homogeneity of
Concrete Admixtures.
(2) Concrete performance test: according to GB 8076-2008 Concrete Admixtures, C50 concrete
performance test is carried out, the admixture contains solid is 15% and content is 1.3%. The concrete
mix can be shown in Table 3:
Table 3 concrete mix proportion Kg/m3
Strength grade C S G1 G2 W Amixture
C50 497 790 200 804 159 5.96

3. Results and Analysis

3.1. The Effect of Mass ratio of Acid to Ether on the Fluidity of PEFA Cement Paste
When the reaction temperature is 20℃ and the concentration of reaction system is 50% (the mass ratio
of H2O2, VC, 30% NaOH, TGA and total mass is 0.3%, 0.09%, 2.5% and 0.12%, respectively, and
the mass ratio of acid to ether is 8.6%, 8.8%, 9.0%, 9.2%, 9.4%, 9.6%, respectively), the test results of
the influence of mass ratio of acid to ether on the fluidity of PEFA cement paste are shown in Figure
1:

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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

Figure 1 effect of mass ratio of acid to ether on fluidity of PEFA cement paste
It can be seen from Figure 1 that with the increase of mass ratio of acid to ether, the initial fluidity
of water purification slurry increases first and then decreases. When the mass ratio of acid to ether is
9.4%, the initial fluidity of cement paste reaches the peak, which is 242mm. After 2 hours of loss, the
fluidity of cement paste is 202, which is larger. When the mass ratio of acid to ether is 9.2%, the
distance between the two broken lines is the shortest. It can be seen that when the mass ratio of acid to
ether is 9.2%, the initial cement paste of PEFA is larger and the loss is smaller.

3.2. The Effect of Temperature on the Fluidity of PEFA Cement Paste

When the concentration of reaction system is 50%, the mass ratio of acid to ether is 9.2%, and other
conditions remain unchanged, PEFA is synthesized at -10℃, 0℃, 10℃, 20℃ and 30℃, respectively.
The test result of the influence of different temperature conditions on the fluidity of cement paste is
shown in Figure 2:

Figure2 effect of temperature on fluidity of PEFA cement paste

It can be seen from Figure 2 that when the reaction temperature is -10℃, the maximum fluidity of
PEFA initial cement paste is 232mm; when the reaction temperature is 30℃, the minimum fluidity of
PEFA initial cement paste is 184mm. The trend of initial cement paste fluidity can be seen, In the
temperature range of -10 ~ 30℃, the initial fluidity of PEFA cement paste decreases with the increase
of reaction temperature, while the fluidity of PEFA increases with the increase of reaction temperature.
When the temperature is 20℃, the distance between the two fluidity broken lines is the shortest. It can
be seen that under the temperature condition, the initial fluidity of cement paste and the fluidity of
2-hour cement paste are optimal.

3.3. The Effect of the Concentration of Reaction System on the Fluidity of PEFA Cement Paste
When the reaction temperature is 20℃, the mass ratio of acid to ether is 9.2%, other conditions remain
unchanged. The influence of reaction system concentration of 35%, 40%, 45%, 50%, 55% on the
fluidity of cement paste is investigated. The test results are shown in Figure 3.

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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

Figure 3 effect of reaction system concentration on fluidity of PEFA cement paste

It can be seen from Figure 3 that with the increase of reaction system concentration may cause
initial fluidity fluctuation of PEFA. When the concentration of reaction system is 45%, the initial
fluidity of PEFA reaches its peak of 240mm. Meanwhile, the fluidity of 2h cement paste decreases
with the increase of reaction system concentration. When the concentration of the reaction system is
around 40%, the two broken lines intersect, which indicates that the 2h difference of fluidity of cement
paste is the smallest, and the fluidity loss is the lowest. It indicates that the process conditions are
optimal under the concentration of the reaction system when the concentration of reaction system is
40%.

3.4. Effect of Dropping Time on Fluidity of PEFA Cement Paste

When the reaction temperature is 20℃, the concentration of reaction system is 40%, the mass ratio of
acid to ether is 9.2%, and other conditions remain unchanged, the test results of the influence of
dropping time 1.0h, 1.5h, 2.0h, 2.5h, 3.0h on the fluidity of cement paste is shown in Figure 4.

Figure 4 effect of dropping time on fluidity of PEFA cement paste

It can be seen from Figure 4 that with the prolongation of dropping time, the initial fluidity of
cement paste gradually decreases, the inflection point appears at 2.5h, and the fluidity of cement paste
slightly increases, while the fluidity of 2h cement paste increases at first and then decreases with the
extension of dropping time. When the dropping time is 2.5h, the difference of fluidity is the smallest
and the distance between the two broken lines is the shortest. When the dropping time is 2.5h, the
process data is the best.

3.5. Concrete Performance Test

According to the above optimal conditions, when the final reaction temperature is 20℃, the
concentration of reaction system is 40%, the reaction dropping time is 2.5h, the mass ratio of acid to
ether is 9.2%, the mass ratio of H2O2, Vc, 30% NaOH solution and TGA to is 0.3%, 0.09%, 2.5% and

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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

0.12%, the workability of the prepared PEFA and PES can be compared. The two superplasticizers can
be diluted to a solution with 15% solid content, and C50 concrete test can be conducted according to
Table3. When the mixing time of concrete mixer is set to 2 min, the observation results of concrete out
of machine state are shown in Figure 5:

(a) drawing of concrete with PES (b) drawing of concrete with PEFA
Figure 5 comparison of the states of concrete out of machine between PES and PEFA
It can be seen from Figure 5 that the concrete mixed with common polycarboxylate water reducer
(PES) has poor concrete fluidity, less paste and thicker concrete, and the stone exposed to the concrete
surface is serious; the concrete with newly synthesized polycarboxylate water reducer (PEFA) has
better fluidity, more slurry and better encapsulation of stone. From the view of concrete state, the
fluidity, cohesiveness and wrapping property of concrete are obviously better after adding the newly
synthesized polycarboxylate water reducer (PEFA), which can solve the problems of difficult
construction and poor workability of concrete.
The slump, expansion, setting time, air content and compressive strength of the above concrete are
tested. The experimental results can be shown in Table 4:
Table 4 test results of concrete performance
Slump/ Expansion Concrete air
(mm/mm) （%） Setting time Compressive strength
Rewindi
Sample (h) (MPa)
ng time
number
（s） Initial Final
Initial 2h 3d 7d 28d
set set
PES 215/565 185/475 2.6 5.4 7.0 9.0 36.4 51.0 58.2
PEFA 230/585 215/520 2.4 3.6 7.0 9.0 36.9 51.6 59.5
It can be seen from the test results in Table4 that the initial slump and expansion of PES concrete
with 15% solid content are 215mm and 565mm respectively; the slump loss and expansion loss of
concrete are 30mm and 90mm respectively after 2h. Compared with the concrete with 15% solid
PEFA admixture, the initial slump and expansion of concrete with 15% solid PEFA admixture are 15
mm larger and 20 mm larger; after 2h of concrete loss, the loss of slump and expansion is smaller, the
slump loss is 15 mm, and the expansion loss is 60 mm. The differences of air content and setting time
of concrete between the two are small, but the compressive strength of concrete with 15% solid PEFA
in 3d, 7d and 28d is slightly higher. It can be seen from the concrete performance test that the new
additive prepared by water reducing and slump retaining polycarboxylate mother liquor (SC) can
greatly improve the fluidity, cohesiveness, wrapping property of concrete, and the working
performance of concrete to a certain extent, which has high use value.

3.6. GPC Analysis

The results of GPC test of PEFA are shown in Table 5.
Table 5 Comparison of GPC data
Conversion
Sample number Mn Mw Mp Mw/Mn
rate %
PES 26715 52362 37526 1.96 91.53

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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

PEFA 25368 43725 34244 1.72 94.24

According to the GPC data test in Table 5, the weight average molecular weight of PES is
relatively large, which is 52,362 with its polydispersity coefficient of 1.96. The average molecular
weight of PEFA is 43,725, with its polydispersity coefficient of 1.72. a relatively narrow molecular
weight distribution and a relatively large conversion rate.

3.7. The Analysis on Infrared Spectrum

The functional controllable polycarboxylate superplasticizer (PEFA) can be analyzed in terms of
infrared spectrum, the result of which can be shown in Figure 6.

Figure 6 infrared spectrum of functional controllable polycarboxylate superplasticizer (PEFA)

As shown in Figure 6, 3,402 cm-1 is the stretching vibration absorption peak of hydroxyl (-OH),
2,874cm-1 is the stretching vibration absorption peak of alkyl (-C-H), 1,466cm-1 and 1,344cm-1 are the
in-plane bending vibration absorption peaks of alkyl (-C-H), 1,723 cm-1 is the stretching vibration
absorption peak of carbonyl (-C=C-CO-O-), and 1,112cm-1 is the stretching vibration absorption peak
of ether bond (-C-O-C). It can be inferred that the structural formula is shown in Figure 7.
H2 H H H H2 H
C C a C C b C C
c
C O C OC O O
ONa ONa ONa
CH2
4

O
CH2
CH2
O
Hd

Polymerization degree:a,b,c and d

Figure 7 structure diagram of functional controllable polycarboxylate superplasticizer

4. Conclusion
(1) Through screening the influence conditions of mass ratio of acid to ether, dropping time, reaction
system concentration and dropping time on the fluidity of PEFA cement paste, it can be seen that,
when the mass ratio of acid to ether is 9.2%, the reaction temperature is 20℃, the concentration of
reaction system is 40%, the reaction time is 2.5h, the mass ratio of H2O2, Vc, 30% NaOH, TGA and
total mass is 0.3%, 0.09%, 2.5%, 0.12% respectively, the process level of the functional controllable
VPEG polycarboxylate superplasticizer can reach its peak. When the dosage of PEFA is 0.23%, the
initial fluidity of cement paste is larger, and the fluidity loss of 2h cement paste is the minimum.

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ICAESEE 2020 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 647 (2021) 012064 doi:10.1088/1755-1315/647/1/012064

(2) The results show that the fluidity, cohesiveness and encapsulation of concrete with PEFA are
better than those with PES. The concrete fluidity is 20 mm larger than that of PES. The concrete
cohesiveness and encapsulation of concrete show that there are no exposed stones on the surface of
concrete, and the slurry is more abundant. The construction performance of concrete can be effectively
improved by adding functional controllable polycarboxylate superplasticizer (PEFA).
(3) According to the GPC data, when the polydispersity coefficient of the synthesized PEFA is 1.72
and the molecular weight distribution is narrower. The results of infrared spectrum show that the
molecular structure of the product has carboxyl, ester, polyoxyethylene, which is consistent with the
molecular structure of the designed water-reducing admixture.

About the author:WenHong Chen, male, undergraduate course, engineer, Engaged in KZJ New
Materials Group (Guizhou) Co., Ltd., mainly engaged in the development and application of concrete
admixtures.
Mailing address: KZJ New Materials Group (Guizhou) Co., Ltd. (551206), Gujiao Town, Longli
County, Guizhou Province.
Contact number:15985110660.
Mailbox：1451861416 @qq.com.

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[3] Liu,L.,Wang,K.L.,Hu,Y.Z.(2010)Influences of Functional Groups and Molecular Structure of
Synthesized Polycarboxyl Superplasticizer on Crack Resistance of Concrete. China Concerete
And Cement Products, 5-8.
[4]Zeng,J.(2015)VPEG Synthesis of VPEG Type PolycaI．boxylate Superplasticizer.Guangzhou
Chemical, 43:105-107.
[5]Lu,Z.M.,Zeng,S.J.,Deng,H. etc. ( 2020)Synthesis and properties of polycarboxylate superplasticizer
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