Applied Mechanics and Materials Vols.

204-208 (2012) pp 3881-3885 Online: 2012-10-26

© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMM.204-208.3881

Synthesis and Characterization of Comb-like Polycarboxylate

Superplasticizer
Yunhui Fang1, a, Zhuojun Jiang1,b ,Yuliang Ke1,c , Xiaolu Chen1,d ,
Feilong Zheng1,e , Zidong Lan1,f , Mengqin Guan1,g , Guangxing Lai1,h ,
Tianxing Lin1,i , and Miaomiao Gui2,j
1
Fujian Prominent New Materials CO.,LTD. , Xiamen, China
2
Xiamen Academy of Building Research Group CO.,LTD. , Xiamen, China
a
fangyunhui@126.com, b jzj0407@tom.com, c keyuliang8207@yahoo.cn, d milunp@yahoo.com.cn,
e f g h
zflpeter@hotmail.com, zdlan99@163.com, guanmengqin880@126.com, lgx502@foxmail.com,
i j
ltxtig@sina.com, mututu@126.com

Keywords: Synthesis, Characterization, Polycarboxylate superplasticizer, Graft, Polymerization

Abstract. Polycarboxylate superplasticizers have become the superstar for high-performance

concrete. Because their molecular structure can be easily manipulated by impart new materials to
acquire new performance. In this paper, the synthetic parameters adjusting experiment is utilized to
get the optimal synthetic formulations. The reaction control factors and polymerization mechanism
are also discussed. After characterization, we concluded that the expected performance of
polycarboxylate superplasticizer could fabricate through radical graft copolymerization reaction by
molecular designing.

Introduction
In the past few years, chemical admixtures such as water reducers have done great contributions to
improve the application performance of concrete. Among these admixtures, polycarboxylate
superplasticizer which exhibits an excellent ability of water–reducing, prevention of slump loss and
easily modifying by changing the combined monomers, have been proven to be the most perspective
and the trend of water-reducers for concrete in the future [1,2].
Conventionally, the polycarboxylate superplasticizer is a kind of comb-like macromolecule
superficial agent, which obtains by unsaturated monomer through the radical graft copolymerization
reaction. In order to obtain polycarboxylate superplasticizer with high properties, the synthetic
method was studied which based on molecular design theory of polymer [3,4].
In this article, the structure of superplasticizer was characterized by FT-IR and GPC. Furthermore,
the effects of the product on fluidity of cement paste and water reduction for concrete were
investigated.

Experiments
Materials. Vinylmethylpolyethylene glycol (VPEG), produced in Liaoyang City, Liaoning Province,
CH2=CH(CH3)CH2CH2O(CH2CH2O)m(CH2CH3CHO)nH; Acrylic Acid (AA), produced in Korea;
Vitamin C (Vc), Hydrogen Peroxide (H2O2), Sodium Formaldehyde Sulfoxylate (SFS), Ammonium
Persulfate (APS) and other synthetic materials are purchased from China Chemical Reagent; Ordinary
Portland cement, P.O 42.5R, produce in Longyan City, Fujian Province; Sand, produced in
Zhangzhou City, Fujian Province; Stone, produced in Xiamen City, Fujian Province.
Synthesis methods. A certain amount of macromonomer，unsaturated monomer and water are
charged in a glass bottom-rounded reactor equipped with mechanical stirrer, thermometer and reflux
condenser. The system is purged with nitrogen and heated at a temperature. After the addition of
initiator and chain transfer agent in 3 hours, the system is further kept at a temperature for one hour
and then neutralized with 30% NaOH. An light-coloured polymer solution are obtained.

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3882 Progress in Industrial and Civil Engineering

FT-IR and GPC analysis. The Fourier transform infrared spectroscopy (FT-IR) spectra in the
range of 4000-400 cm-1 were obtained with the KBr plates by using Nicolet Avator 360. Gel
permeation chromatography (GPC) measurements were performed at 30℃ with ultrapure water as the
eluant (1.0 ml/min) using an Waters 1515 HPLC System.
Performance testing method. Test flow of cement mortar for workability according to
GB8077/T-2000＜Methods for testing uniformity of concrete＞. Test concrete slump and its loss
according to GB8076-2008＜Concrete admixture＞.

Results and discussion

Influences of initiator system and its amount on the performance
The influences of three kinds of initiator system on the properties, which are Vc/H2O2, SFS/H2O2
and APS, have been investigated. The general polymerization rate constant K is usually calculated by
Arrhenius formula (K=Ae-E/RT) [5]. Initiator decomposition activation energy (Ed) is predominant in
polymerization activation energy, so the radical graft copolymerization reaction temperature is up to
the value of Ed. The redox system decomposition activation energy is lower than the peroxide system,
so the former one can keep higher polymerization rate in lower temperature, while the latter one needs
higher reaction temperature.
The effect of paste fluidity to the polycarboxylate superplasticizer from different initiator dosage
was shown in Fig.1.

260 Vc
)
m
m SFS
(
y 220 APS
t
i
d
i
u 180
l
f
e
t 140
s
a
P
100
0.25 0.5 0.75 1 1.25 1.5 1.75 2
Initiator(%)
Figure 1 The effect of paste fluidity to the polycarboxylate superplasticizer from different initiator
dosage

Upon previous work, the temperature of Vc/H2O2, SFS/H2O2 and APS initiator system was
respectively chose at 55℃, 60℃ and 90℃. When the dosage of Vc was 0.75% and the mole ratio of
Vc and H2O2 is 1:4, the paste fluidity reached the highest. The paste fluidity decreased amide
increasing of the Vc dosage. The disperse performance of polycarboxylate superplasticizer which
prepared by SFS/H2O2 and APS initiator system behaved worse than the one prepared by Vc/H2O2
initiator system. So the optimized initiator system was Vc-H2O2 and the best dosage was 0.75%. To
find out its cause, the main reason might be the reactive activity of Vc-H2O2 initiator system matches
to the macromonomer，unsaturated monomer. So it was more likely to format copolymer which had
been certified to excellent performance, but not homopolymer.
Influences of polymerized concentration on the performance
The variation in paste fluidity was similar and much smaller when the polymerized concentration
altered from 30% to 50%. While disperse performance decreased obviously when the polymerized
concentration exceed 60%, especially 70%. The experimental data was shown in Fig.2.
 Applied Mechanics and Materials Vols. 204-208 3883

300
) 0h
mm
(y 250 1h
t
id
iu 200
lf
et 150
sa
P
100
30 40 50 60 70
Polymerized concentration(%)
Figure 2 The effect of paste fluidity to the polycarboxylate superplasticizer from different
polymerized concentration
The viscosity of the synthetic system was too low to be hampered the spread of monomer in the
early polymerization stage. The influence of polymerized concentration on the radical graft
copolymerization reaction intensified continually along with the prolonging of reaction time.
Gradually, the chain end rearrangement became blocking, and the activity end got embedded. It would
give rise to abort polymerization eventually. Everything taking into consideration, the best
polymerization concentration was 50%.
Influences of monomer feed ratio on the performance
The monomer feed determined the final large measure molecular structure of polycarboxylate
superplasticizer. The achieved experiment result which was shown in Fig.3, namely, the paste fluidity
improved with the adding the dosage of AA (represented by feed mole ratio AA: VPEG). It was
speculated as that the back bone charge density of polycarboxylate superplasticizer molecules was
further increased with increasing the dosage of AA. It brought about the adsorption of
polycarboxylate superplasticizer increasing in the early stage of hydration, for reason that charge
exclusion function can separate cement particle and water which exhibits disperse elevating on
macroscopic performance. When further increasing the dosage of AA, the main chain charge density
would be too dense, which the charge of back bone would influence mutually, the adsorption on the
cement particle declined and the performance deteriorated. So the best feed ratio was AA: VPEG =
1:4.

300
)m 0h
m(
yt260 1h
id
iu220
lf
et180
sa
P
140
2.75 3 3.25 3.5 3.75 4
feed ratio
Figure 3 The effect of paste fluidity to the polycarboxylate superplasticizer from different feed ratio
(AA/VPEG, mole)

Concrete performance test

After a series of synthetic parameters optimization ， the comb-like branched structure of
polycarboxylate superplasticizer was synthesized. The concrete mixture ratio was as follows: cement
(C): fly ash (FA): sand (S): stone (G) = 440:84:644:1052, water cement ratio=0.34. The experimental
results were shown in Table 1.
3884 Progress in Industrial and Civil Engineering

Table 1 Concrete experiment of polycarboxylate superplasticizer

Water-reducing Air content Slump (mm) Compressive strength (MPa)
Sample
Rate (%) (%)
0h 1h 7d 28d
Blank / 1.7 210 165 19.7 33.4
Polycarboxylate
34.2 2.9 210 200 26.8 46.5
superplasticizer

From table 1, the synthetic product had very high water-reducing rate to 34.2%. We could conclude
that the concrete without addition polycarboxylate superplasticizer displayed worse than the one
addition polycarboxylate superplasticizer in freshly mixed concrete and hardened concrete.
Structural characterization
The analysis of chemical structure was carried by FT-IR and GPC. Fig.4 was the FT-IR spectra of
the synthetic polycarboxylate superplasticizer. Fig.5 was the GPC spectra of polycarboxylate
superplasticizer. The GPC result was shown in Table 2.

95

64 22.
64. .5
58 88. 345
90 024 52. 48
3.4 725 1
61 1 982 55
92 1 .0
85 251 19
5.5 .1
41 33 59
.1
80 53
1
T
% 06
45
75 6.2 .4
43 78
2

70

65

60 13
.3
01
1
55
4000 3000 2000 1000
Wavenumbers (cm-1)

Figure 4 FT-IR spectra of polycarboxylate superplasticizer

In Fig.4, The signals at 2874.54 cm-1 are attributed to -CH3- and -CH2-. The signals at 1643.85 cm-1
are assigned to –COOH. The peaks at around 1455.29 cm-1 stands for -CH2- and 1351.33 cm-1 stands
for -CH3-. The ether group (-O-) appears about 1103.31 cm-1.
From Fig.5 and Table 2, the product has two major peaks. One peak’s MP value is 120331, while
the other’s value is 2752. The copolymer product exhibits excellent fluidity due to its long chain
structure, because the long chain structure gives space repulsion resistance in the slurry of cement and
water.

Figure 5 GPC spectra of polycarboxylate superplasticizer

 Applied Mechanics and Materials Vols. 204-208 3885

Table 2 GPC result of polycarboxylate superplasticizer

Peak Retention Time (min) Mn Mw MP Mz Mz+1 Area (%)
1 6.091 55303 93319 120331 127704 150490 73.82
2 8.900 1118 3951 2752 6673 8486 26.18

The polycarboxylate superplasticizer contains hydrophilic main chain and hydrophobic

polyethylene oxide (PEO) side chains, consisting of a certain proportion of hydrophilic and
hydrophobic groups. The analysis shows that polycarboxylate superplasticizer links segments with
ether and expectations of molecular structure. The schematic diagram is shown in Fig.6 [6]. Therefore
it can fabricate the expected performance through radical graft copolymerization reaction by
molecular designing with selecting the appropriate response monomers and reaction conditions.
CH2 CH

CH2

O CH2 CH2O CH3

n
Figure 6 Chemical structure of polycarboxylate superplasticizer

Conclusions
(1) Through the experimental parameters adjustment, the optimal radical graft copolymerization
reaction conditions were as follows: 55℃, 0.75% dosage of Vc , Vc : H2O2 = 1:4, 50% polymerization
concentration, AA: VPEG = 3.25.
(2) The synthetic comb-like polycarboxylate superplasticizer had very high water-reducing, and
could improve the workability performance of freshly mixed concrete and compressive strength of
hardened concrete.
(3) The polycarboxylate superplasticizer contains hydrophilic main chain and hydrophobic
polyethylene oxide side chains, which can fabricate the expected performance through radical graft
copolymerization reaction by molecular designing.

References
[1] K. Yamada, S. Ogawa, T. Takahashi: 2nd international RILEM symposium on self compacting
concrete, Tokyo (2001), p. 159-168.
[2] J. Plank, B. Sachsenhauser, J. de Reese: Cem. Concr. Res. Vol 40 (2010), p. 699-709.
[3] K. Yamada, T. Takahashi, S. Hanehara, M. Matsuhisa: Cem. Concr. Res. Vol 30 (2000) , p.
197-207.
[4] F. Burank, S. Hasan: Constr. Build. Mater. Vol 22 (2008), p. 1972-1980.
[5] Z.R. Pan: Polymer chemistry (Third edition)(Chemical Industry Press, Beijing 2003), in Chinese.
[6] Y.H Fang, X.X Ma, M.M Gui, T.X. Lin: Concrete. Vol 254(2010), p.73-74, in Chinese.
Progress in Industrial and Civil Engineering
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Synthesis and Characterization of Comb-Like Polycarboxylate Superplasticizer

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