Synthesis of Montmorillonite/Acrylic Acid/Acrylamide Tricopolymer and Its Super Absorbent Properties

Synthesis of Montmorillonite/Acrylic Acid/Acrylamide Tricopolymer

and Its Super Absorbent Properties
Xiao-yuan Zhan1,2, Fang Wang, Xing-wei Li, and Min Wang
1
College of Material Science and Engineering, SDUST, Qingdao, Shandong 266510, China
2
State Key Laboratory of Mining Disaster Prevention and Control, SDUST, Qingdao, Shandong 266510, China

Summary
Montmorillonite/acrylic acid/acrylamide tricopolymer was synthesized by using aqueous solution polymerization.
Some factors affecting the water absorbency of super absorbent composite material, such as the neutralization
of acrylic acid, the amount of added montmorillonite, initiator and crosslinking agent were investigated. The
best formula for absorbing the running water was proposed, it included 40% montmorillonite, 80% monomer
neutralization degree, 0.08% crosslinker amount, and 0.15% initiator, and the water absorbency of the obtained
composite materials was 150 times. The FTIR research indicated that montmorillonite was effectively compounded
with polymer, it is found that the composite with a good water retention and heat resistance is significant for
reducing the product cost and improving the comprehensive property of the composite.

Keywords: Super absorbent, Montmorillonite, Sodium poly-acrylate, Composite

1. Introduction
Super absorbent polymer(SAP) is
one kind of polymer contains a
large amount of strong hydrophilic
groups, such as -OH, -COOH,
which has special structure with
copolymerization crosslinking. This
polymer can absorb abundant water
compared with general water absorbing
materials in which the absorbed water is
hardly removable even under pressure.
The traditional SAP is formed by
hydrophilic group of alkene complex,
which is widely used in modern
daily life. However, there are some
drawbacks, for example, high material
cost, low gel strength, poor water
retention and poor biodegradability. In
view of aforementioned disadvantages,
people have committed themselves to
the development of the SAP functional
research for a long time1, specially super
absorbent mineral/polymer composite.
©
Smithers Information Ltd., 2014
Super absorbent mineral is mainly
various natural inexpensive clay
mineral with certain reactive functional
groups, for instances, montmorillonite,
kaolinite, attapulgite (surface contains
a lot of “ OH”, “Si-O” and other
reactive groups), which act as the graft
section of base resign material. Super
absorbent mineral can not only reduce
the cost of traditional SAP raw material,
but also can improve their defects.
Therefore, it is currently becoming
an important research direction to
prepare excellent composite SAP
material. Super absorbent mineral/
polymer composite can be applied as
water-retentive material in fields of
dry farming, gardening, ecological
environment management, also used in
coal mines to do as anti-extinguishing
materials by virtue of its low cost,
high strength and good salt resistance.
In the practice of fighting mine fires,
pumping water, mud, inorganic salts
inhibitor, inert gas and foam had been
used with certain unideal effects2. Take
advantage of the good water retention
of super absorbent polymer for fighting
fire, when sprayed into the mouth, it
can realize flame extinguishing due
to water evaporation. In the case of
non-spontaneous combustion, the
SAP can absorb water vapor in the
roadway, cover the coal well, cut
off the interaction between coal and
oxygen, then achieve the purpose of
fire prevention and control.
Domestic researchers Zhou Meng3,
Lin Jianming4, Wei Yuelin5, Wan Tao6
had used montmorillonite (bentonite)
and acrylic acid (acrylamide/starch)
as raw materials to successfully
synthesize super absorbent composite
materials with special features in raw
materials ratio, synthesis process
and properties characterization. This
article described the preparation and
water absorbency of montmorillonite/
acrylic acid/acrylamide tri-copolymer
in detail. Some factors affecting the
performance of this tricopolymer, such
as the neutralization of acrylic acid,

Polymers & Polymer Composites, Vol. 22, No. 5, 2014 489

 Xiao-yuan Zhan, Fang Wang, Xing-wei Li, and Min Wang
the amount of added montmorillonite,
initiator and crosslinking agent were
investigated. Then it is found that the
composite with a good water retention
and heat resistance is significant
for reducing the product cost and
improving the comprehensive property
of the composite.
2. Experiment
2.1 Experimental Materials
• Montmorillonite, purity of 90%-
98%, industrial grade, Qingdao
Yu z h o u C h e m i c a l l i m i t e d
Company;
• Acrylic acid (C2H4O2), AA, purity
≥ 99.5%, AR, Tianjin Damao
Chemical Reagent Factory;
• Acrylamide (C2H5NO), AM, purity
of 98.0%, AR, Tianjin Guangfu
Fine Chemical Research Institute;
• Sodium hydroxide (NaOH), CP,
Tianjin Damao Chemical Reagent
Factory;
• Crosslinking agent: N,
N-methylene-bis-acrylamide
(C 7 H 10 N 2 O 2 ), MBA, purity ≥
98.5%, Chengdu Kelong Chemical
Reagent Factory;
• Initiators: potassium persulfate
(K2S2O8), AR, Tianjin Chemical
Reagent Sixth Factory.
2.2 Preparation of the Super
Absorbent Polymer
The process starts by dispersing
appropriate amount of montmorillonite
into a beaker containing some deionized
water, then placing the beaker in an
ultrasonic cleaner to sufficiently disperse
and adding an appropriate amount of
acrylic acid and acrylamide after cooling.
Separately, NaOH is dissolved in the
mixture in order to neutralize C2H4O2
and mixed with K2S2O8 and C7H10N2O2.
It is then placed into a thermostatic water
bath to the sufficiently reaction. Finally,
the production obtained is cut into small
pieces and placed into a drying oven
at 110 °C to get the super absorbent
material.
490
2.3 Measurement of the Water
Absorbency7
A common method of measuring water
absorbency is filtration. The typical
behavior begins by dissolving 0.50 g
of super absorbent composite material
in water within a 1000 ml beaker in
order to saturate. Prior to use, this gel
must be filtrated for adequate time with
0.15 mm (100 mesh) sieve and placed
the gel on the mesh for 15 min. At last,
we calculate its water absorbency by
the following formula:
Water absorbency = the quality of
the gel after absorbing water/ the
quality of the gel
3. Results and
discussion
3.1 Effect Factors on Water
Absorbency
3.1.1 The Amount of Added
Montmorillonite
Montmorillonite is one kind of
hydrophilic inorganic mineral
materials which can inflate to 10 to 30
times when it absorbs water8. But with
respect to super absorbent polymer,
its water absorbency is extremely
low. However when combines it with
organic polymer, its water absorbency
Figure 1. The effect of the amount of montmorillonite on water absorbency
Polymers & Polymer Composites, Vol. 22, No. 5, 2014
will be greatly improved, also the cost
of product be multiply increased. To
seek the best balance between cost and
water absorbency, fixed acrylic acid and
acrylamide in a mass ratio of 2:1, 80%
monomer neutralization degree, 0.08%
crosslinker amount, and 0.15% initiator
were added to synthesize the super
absorbent polymer. Then we studied
the influence of the amount of added
montmorillonite on water absorbency.
As we can see from Figure 1, the
water absorbency decreases along with
increasing amount of montmorillonite,
but when the added amount exceeds
40%, the decreased tendency becomes
somewhat gentle. Due to the high
amount of added montmorillonite, the
cost of super absorbent composite can
be greatly reduced.
3.1.2 Initiator
Initiator can promote the activity
of monomers that involved in the
poly-reaction. The higher activity of
monomers that more difficult to control
the poly-reaction process is easier
to form highly crosslinked polymer,
which lead to lower water absorbency.
If the activity of monomers is low,
then the response time prolongs and
the degree of crosslinking lessens, so
that the water soluble property will
increase, but the water absorbency
 Synthesis of Montmorillonite/Acrylic Acid/Acrylamide Tricopolymer and Its Super Absorbent Properties

will decrease. To study the effect of and water retention is poor. On the absorbency is fine when the amount
added initiator, fixed acrylic acid and contrary, the water absorbency also is is 0.06% and it attains the maximum
acrylamide in a mass ratio of 2:1, 80% low when the amount of crosslinking while the amount reaches to 0.08%10.
monomer neutralization degree, 0.08% agent is extra high. Therefore
crosslinker amount, and 0.15% initiator controlling the appropriate amount
3.2 Performance of the Super
were added to synthesize the super of crosslinking agent is one pivotal
factor to successfully synthetise super
Absorbent Polymer
absorbent polymer. Figure 2 displays
that the variation of water absorbency absorbent polymer. To study the effect On the basis of those factors affecting
from increased to decreased along with of crosslinking agent, fixed acrylic acid water absorbency of super absorbent
added initiator amount. And the water and acrylamide in a mass ratio of 2:1, composite material, such as the
absorbency reaches to the best when 80% monomer neutralization degree, neutralization of acrylic acid, the
the amount is 0.15%. 0.08% crosslinker amount, and 0.15% amount of added montmorillonite,
initiator were added to synthesize initiator and crosslinking agent were
3.1.3 The Neutralization of Acrylic the super absorbent polymer. It is investigated. The best formula for
illustrated from Figure 4 that the water absorbing water was proposed, it
Acid
We can learn that electric charge density
of material is an important factor which Figure 2. The effect of initiator on water absorbency
affects water absorbency by Flory’s
swelling theory. The reason why super
absorbent polymer has high water
absorbency is because of the presence
of different hydrophilic groups. As
to the montmorillonite/acrylic acid/
acrylamide tricopolymer, -COO- is
superior to -COOH, therefore the
neutralization degree has becoming a
great factor effects on water absorbency.
The super absorbent polymer shows
good water absorbency due to the
interactions between functional groups
when the degree of neutralization and
the proportion of -COOH, -COONa,
and -CONH2 in the polymer chain
are appropriate. To study the effect
of neutralization, fixed acrylic acid
and acrylamide in a mass ratio of 2:1,
80% monomer neutralization degree, Figure 3. The effect of neutralization degree on water absorbency
0.08% crosslinker amount, and 0.15%
initiator were added to synthesize the
super absorbent polymer. As we can see
from Figure 3, the water absorbency
keeps increasing as the degree of
neutralization from 60% to 80%, but
has no significant increase when the
degree is over 80%.

3.1.4 Crosslinking Agent

In the synthetic process of super
absorbent polymer, the less amount
of crosslinking agent is, the less dense
it is. Because of poor crosslinking
among monomers, the formative
network structure is relatively simple,
then its water absorbency is low

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 Xiao-yuan Zhan, Fang Wang, Xing-wei Li, and Min Wang

included 40% montmorillonite, 80%
monomer neutralization degree,
0.08% crosslinker amount, and
0.15% initiator, then measured its
performance.
3.2.1 Fourier Transform Infrared
Spectroscopy (FTIS)
From Figure 4 and Table 1, it is quite
clear that the sample reserves some
absorption peaks of montmorillonite:
the water between silicate layers
bending, stretching and vibrating at
3427 cm-1, the O-H swing nearby
917 cm-1 and 624 cm-1, the Si-O
crooking and vibrating. Above
characteristics shows that the structure
Figure 4. The effect of crosslinker on water absorbency
of montmorillonite still exists after
polymerization. However, the hydroxy
bending, stretching and vibrating
became wide and strong in the high
frequency area of 3427 cm-1.That
was explained probably generating
hydrogen bonds under the effect
of acrylic hydroxy vibrating which
inserted into silicate layers. Meanwhile
wide and strong absorption peaks of
1675 cm-1 (carbonyl) and 1573 cm-1
(carboxylate) took the place of
1636 cm-1.In the same time, there were
characteristic peaks of 1459 cm-1 and
1413 cm-1 which caused by the -COOH-
symmetrical bending, stretching
and vibrating at low frequency area
nearby. It showed that some chemical
bonds took place between acrylate and
montmorillonite, and then effected
the water bending, stretching and
vibrating. Simultaneously there were
characteristic functional groups of
acrylamide what meant the super
absorbent polymer was synthetised
following the effective polymerization
reaction of montmorillonite, acrylic
acid and acrylamide.
3.2.2 Thermal Gravimetric Analysis
(TGA)
Figure 6 displays that there is a
big but narrow endothermic valley
nearby 110° for the reason that the
super absorbent polymer releases
absorbed water when heated. And
the TGA curve tends to smooth from
200 to 350°. A wide exothermic peak
appears at 650° caused by organic
decomposition and combustion that
lead to structural damage. It is shown
from the TGA curve that continuous
weight loss (water release and organic
decomposition). This particular sample
ultimately happens to contain a
invariable amount at 40 wt.%, hence,
adding montmorillonite at the mount
of 40% in the process of synthetising
the super absorbent polymer.

3.2.3 Measuring Water Absorbency

The method begins by pulverizing the
synthetic super absorbent polymer
in a sieve (100 mesh) and drying to
constant weight at 110°. Afterwards,

Table 1. The FTIR spectra of the characteristic functional groups of the super absorbent resin
Wavenumbers Mode of vibration Functional group
3330~2500cm -1
O—H bending, stretching and vibrating O—H in carboxylic acid
2940 cm-1 C—H bending, stretching and vibrating C—H in carboxylic acid
1725~1695 cm-1 C＝O bending, stretching and vibrating C==O absorption spectrum in carboxylic acid
1430 cm -1
O—H outward bending vibration O—H in carboxylic acid
1250 cm-1 C—O bending, stretching and vibrating C—O in carboxylic acid
1616~1540 cm -1
—COO-anti-symmetrical bending, stretching and vibrating —COO- in carboxylate
1450~1400 cm-1 —COO- symmetrical bending, stretching and vibrating —COO- in carboxylate
3450~3225 cm -1
NH2 bending, stretching and vibrating NH2 in primary amides
1690~1610 cm-1 C＝O bending, stretching and vibrating C＝O absorption spectrum in amides
1620 cm-1 NH2 transformative vibrating NH2 in primary amides
700~625 cm -1
NH2 outward bending vibration NH2 in primary amides

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 Synthesis of Montmorillonite/Acrylic Acid/Acrylamide Tricopolymer and Its Super Absorbent Properties

it is placed into 1000 ml water and Figure 5. The FTIR spectra of the super absorbent resin
weigh its absorbed weight every half
hour. As we can see from Figure 7,
the super absorbent polymer reaches
to constant weight after 4 hours and
its water absorption ratio is 150 times.

4. Conclusions
Montmorillonite/acrylic acid/
acrylamide tricopolymer was
synthesized by using aqueous solution
polymerization which was simple
and easy to operate. The best formula
for absorbing the running water
was proposed, it included 40%
montmorillonite, 80% monomer
neutralization degree, 0.08%
crosslinker amount, and 0.15%
initiator, and the water absorbency of Figure 6. The thermal gravimetric analysis and differential thermal analysis of
the obtained composite materials was the super absorbent polymer
150 times after 4 hours. Associating
organic monomers with hydroxy in
montmorillonite can improve the
performance of the super absorbent
composite and reduce its cost.

Acknowledgements
This work was supported by
National Program on Key Basic
Research Project(973 Program)(N0.
2012CB723104) and Postgraduate
Fund of Science and Technology
Innovation of Shandong University
of Science and Technology(No.
YC130341).
Figure 7. The water absorption ratio of the super absorbent resin
References
1. Fan Liren, Xu Zhiliang, and Shen
Shangyue, Research progress in
mineral/polymer super absorbent
composites. Journal of Functional
Materials, 36(12) (2005) 1827-
1830,1836.
2. Xu Mangui, Xu Jingcai, Wen Hu,
et al., Current research status of
mechanism and extinguishing
methods of spontaneous combustion
of coal mine, Journal of Xi’an
University of Science & Technology,
21(1) (2001) 4-7.
3. Zhou Meng, Lin Jianming, and Wu
Jihuai, Synthesis and property of
clay-organic resin super absorbent

Polymers & Polymer Composites, Vol. 22, No. 5, 2014 493

 Xiao-yuan Zhan, Fang Wang, Xing-wei Li, and Min Wang
composite, China Mining Magazine,
9(2) (2000) 72-74.
4. Lin Jianming, Yang Zhenfang, Pu
Minli, et al., Research on bentonite/
polyacrylic acid sodium salt super
absorbent composite, Mineralogica
Sinica, 21(3) (2001) 427-430.
5. Wei Yuelin, Wu Jihuai, Huang
Yunfang, et al., Synthesis and surface
modification of kaolin/poly(acrylic
acid) super absorbent composite,
China Mining Magazine, 25(4)
(2005) 379-384.
494
6. Wan Tao, He Wenqiong, Xi
Quanshou, et al., Study on bentonite
composite polysodium acrylate-
acrylamide high water-absorbing
copolymer resin by inverse
suspension polymerization, China
Elastomerics, 13(2) (2003) 8-12.
7. Feng Qiming, Wang Weiqing, Li
Jinli, Synthesis and properties
of bentonite/acrylic resin water-
absorbent & retaining agent, Non-
Metallic Mines, 32(6) (2009) 6-9, 60.
Polymers & Polymer Composites, Vol. 22, No. 5, 2014
8. Wang Hongxi, Bentonite, Beijing:
Geological Publishing House, 1980.
9. Flory P.J. Principles of Polymer
Chemistry, New York: Cornell
University Press, 1953.
10. Wu Jihuai, Wei Yueling, and Lin
Jianming, Preparation of a starch-
graft-acrylamide/kaolinite super
absorbent composite and the
influence of the hydrophilic group
on its water absorbency, Polymer
International, 52 (2003) 1909-1912.