Polymer International

Polym Int 50:946951 (2001)

DOI: 10.1002/pi.721

Synthesis of novel superabsorbing copolymers

for agricultural and horticultural applications
K Mohana Raju* and M Padmanabha Raju
Synthetic Polymer Laboratories, Department of Polymer Science, Sri Krishnadevaraya University, Anantapur-515 003, India

Abstract: A series of novel superabsorbent copolymers (SAPs) based on monomers acrylamide,

calcium acrylate and sodium acrylate have been prepared using ammonium persulfate as initiator and
N,N-methylene-bis-acrylamide (MBA) as crosslinking agent; the monomer concentration, MBA
concentration and initiator concentration were varied. The experimental results show that the SAPs
have good absorbency both in water and NaCl solutions. The copolymers were characterized by IR
spectroscopy. Water retention in soil is enhanced by use of these superabsorbents. The effect of SAPs
on the growth of bean plants is reported. SAPs may be of use as water management materials for
agricultural and horticultural purposes in desert and drought-prone areas.
# 2001 Society of Chemical Industry

Keywords: superabsorbent copolymers; acrylamide; crosslinking agent; swelling capacity; water retention

INTRODUCTION

Superabsorbent copolymers (SAPs) can absorb large

amounts of water during a short period of time. The
absorbed water can be retained even under pressure.
Therefore, SAPs have great advantages over traditional water-absorbing materials such as cotton, pulp
and sponge, and have found a variety of valuable
applications.14 Superabsorbents are used widely in
sanitary goods such as disposable nappies, hygienic
napkins, soil for agriculture and horticulture, gel
actuators, water-blocking tapes, drug delivery systems
and absorbent pads.58 In such applications, water
absorbency and water retention are essential. Some
workers have modied these SAPs in view of enhancing their absorbency, gel strength and absorption
rate.815 The inuence of various reaction parameters
on the water absorption capacity of SAPs has been
investigated by various workers.16,17 The dependence
of water absorbency of SAPs on particle size and
salinity was also investigated by Omidian et al 18 who
found that as the particle size became smaller, the rate
of absorption and ultimate degree of absorption both
increased. Tests of SAPs for agricultural applications
have shown encouraging results because they have
been observed to help reduce irrigation water consumption, lower the death rate of plants, improve
fertilizer retention in the soil and increase plant growth
rates.19 In this direction the authors have done some
work on the synthesis of SAPs and gels that have been
tried for the growth of groundnuts and croton plants
and reported the results in the literature.20,21
In the present investigation the authors report the
synthesis of SAPs by polymerizing acrylamide (AM)

with calcium acrylate (CA) and sodium acrylate (SA).

The copolymers were characterized by IR spectroscopy. The swelling behaviour of the SAPs was studied
with respect to crosslink density, initiator concentration and monomer ratios. The effect of SAPs on the
water retention capacity of soil was also studied.

EXPERIMENTAL
Materials

AM was puried by recrystallization from benzene.

Ammonium persulfate (APS) was recrystallized from
water. N,N-Methylene bisacrylamide (MBA) (chemically pure) was used as purchased. Ethylene glycol
dimethacrylate (EGDMA) and diallyl phthalate (DP)
were used as crosslinking agents after removing the
stabilizer with 2% NaOH solution. All solutions were
prepared with twice distilled water. All solvents were
distilled before use. Calcium acrylate (CA) and
sodium acrylate (SA) were prepared in the laboratory.
Preparation of calcium acrylate (CA)
Calcium oxide (0.5 mol) was dispersed in methanol.
Acrylic acid (0.1 mol) was placed in a conical ask with
dry ether and titrated with the calcium oxide suspension. A white solid separated out. The product was
ltered under vacuum and dried in a vacuum
desiccator. The reaction may be summarized as
follows:
2CH2 CHCOOH CaO ! CH2
Ca # H2 O:

CHCOO2

* Correspondence to: K Mohana Raju, Synthetic Polymer Laboratories, Department of Polymer Science, Sri Krishnadevaraya University,
Anantapur-515 003, India
Contract/grant sponsor: UGC, New Delhi; contract/grant number: F.14-15/97 SR-1
(Received 23 June 2000; revised version received 1 March 2001; accepted 2 April 2001)

# 2001 Society of Chemical Industry. Polym Int 09598103/2001/$30.00

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Novel superabsorbing copolymers

Preparation of sodium acrylate (SA)

Sodium carbonate (0.5 mol) solution was prepared in
distilled water and titrated against acrylic acid
(0.1 mol) placed in a conical ask in dry ether. The
white solid which separated out was recovered under
vacuum and dried in a vacuum desiccator. The
reaction was
2CH2 CHCOOH
Na2 CO3 !2CH2
# H2 O CO2 "

CHCOONa

Synthesis of SAPs

A series of SAPs was prepared using the following

procedure. All reactions were conducted in a threenecked ask equipped with a mechanical stirrer,
condenser and nitrogen line. A weighed quantity of
monomers together with crosslinking agent dissolved
in distilled water was placed in the reaction vessel.
After 15 min stirring, ammonium persulfate was added
to the reaction mixture and then the temperature was
raised slowly to 80 C with stirring. After 2 h of
reaction, a gel was formed. The gel was washed with
ethanol and water and then dried in a vacuum oven at
60 C to constant weight. The dried gel was reweighed
and milled through a screen. All gels are transparent.
Water absorbency measurement22

A sample (1 g) of the SAP was immersed in water (or

saline solution) at room temperature until equilibrium
was reached. The absorbability was determined by
weighing the swollen gel after it had been allowed to
drain on a sieve for 10 min. The water absorbency Q (g
H2O/g sample) was calculated using the following
equation:
m m0
Q g H2 O/g sample
m0
Absorbency is expressed in grams of water retained in
the gel per gram of dried gel; m and m0 denote the
weight of the gel swollen by water and the weight of the
absorbent, respectively.
RESULTS AND DISCUSSION

Table 1 illustrates the absorption capacity of copolymers as a function of monomer distribution in the
copolymer network. Swelling increases with the
increase in ionic units (or monomer ratio) in the
polymer backbone chain, but an excess of ionic units
leads to an increase in the solubility of the copolymer
at a xed crosslinker concentration while its absorption capacity for water is decreased.

Table 1. Influence of the monomeric ratios on the swelling

capacity of crosslinked poly(AMCASA) superabsorbentsa

Monomer in feed
(mol l 1)

Polymer
code

AM

CA

SA

(g H2O/g sample)
Q

S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14

0.80
0.80
0.80
0.80
0.80
0.80
0.80
0.80
0.80
0.80
0.80
0.80
0.80
0.80

0.06
0.14
0.20
0.24
0.28

0.20
0.22
0.24
0.26
0.30

0.06
0.12
0.16
0.18
0.16
0.16
0.16
0.16
0.16

94
150
206
180
164
76
98
126
94
264
320
384
316
252

a
Reaction conditions: crosslinker [MBA] = 5.8  10 3 mol l 1,
initiator [APS] = 3.2  10 3 mol l 1, temperature 80  1 C, reaction time 2 h.

unit, 1719 cm 1 corresponding to nC=O of the

acrylate unit and 1675 cm 1 corresponding to the
carbonyl group of the acrylamide unit. In addition to
the above, peaks are also observed at 1232 and
1174 cm 1 corresponding to COC stretching
interactions of ester groups. The IR analysis indicates
that all the monomeric units (AM, SA and CA) are
incorporated in the copolymer backbone. Figure 1
shows the IR spectra of the copolymer having maximum absorbency.
Thermal analysis

Differential scanning calorimetry (DSC) of the copolymers was carried out using a Perkin Elmer DSC-4
differential scanning calorimeter with a Perkin Elmer
thermal analysis data station mode TADS-101.
The DSC of sample S12 is shown in Fig 2. The
temperature at the maximum point of the DSC curve
was taken as the glass transition temperature (Tg).
This copolymer has a Tg of 219.5 C. The higher value
of Tg indicates that this particular copolymer has a

IR spectra

The IR spectra of the copolymers were recorded on a

Bio-Rad WIN FTIR using KBr pellets. They show the
peaks corresponding to the functional groups attached
to the monomer units. Those observed are 3571 cm 1
corresponding to the nNH stretching of the acrylamide
Polym Int 50:946951 (2001)

Figure 1. Infrared spectrum of poly(AMCASA) (S12).

947

K Mohana Raju, M Padmanabha Raju

Figure 2. DSC curve for poly(AMCA

SA) (S12).

higher crosslinking density. As the crosslinking density

increases, the free volume of the material decreases
and the Tg increases correspondingly.
The thermal stablity of the dry sample was
measured using a Universal V1.12E thermogravimetric analyser (TGA) instrument.
The temperature range covered was 50800 C at a
heating rate of 20 C min 1 using dry nitrogen at a ow
rate 50 ml min 1.
The TGA of sample S12 is shown in Fig 3. There is a
very small weight loss below 100 C, implying loss of
moisture. The sample has signicant weight loss at
200 C (10.7%) and at 300 C (21.5%). The major
weight loss started at 350 C (27%) and the sample
continued to lose weight up to 400 C, with a loss of
50%. Therefore this particular sample has an initial
decomposition temperature of 350 C.

Influence of parameters on water absorbency

The key properties of superabsorbent polymers are the

swelling capacity and the elastic modulus of the
swollen crosslinked gel, both of which are related to
the crosslink density of the network.
Effect of crosslinking agent

Figure 4 shows the water absorbency of crosslinked

poly(AMCASA) as a function of crosslinker concentration. The water absorbency increases as MBA
concentration
increases
from
1.8  10 3
to
3
1
5.8  10 mol l
but decreases considerably when
the
MBA
concentration
is
higher
than
5.8  10 3 mol l 1 because of the decreasing space
between the copolymer chains when crosslinking
increases. The swelling capacity increases as the
EGDMA concentration increases from 1.8  10 3 to

Figure 3. TGA curve for poly(AMCA

SA) (S12).

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Polym Int 50:946951 (2001)

Novel superabsorbing copolymers

Figure 4. Influence of crosslinker concentration on water absorbency (Q)

of poly(AMCASA) (S12) in deionized water.

7.5  10 mol l
but decreases considerably when
the EGDMA concentration is higher than
7.5  10 3 mol l 1. The swelling capacity increases as
the DP concentration proceeds from 1.8  10 3 to
9.0  10 3 mol l 1 but decreases considerably when
the
DP
concentration
is
higher
than
9.0  10 3 mol l 1. The concentration at which the
maximum absorbency of the copolymer occurs depends upon the nature of the crosslinking agent.
Figure 4 shows that the maximum absorbency is found
when the concentration of MBA reaches
5.8  10 3 mol l 1, whereas absorbency is at a maximum at 7.5  10 3 mol l 1 and 9.0  10 3 mol l 1 for
EGDMA and DP, respectively. Further it is also
noticed that maximum absorbency is found when
MBA is used as crosslinking agent because of its more
polar nature. As the concentration of the crosslinking
agent increases the swelling capacity of the copolymer
increases up to a certain level, but with higher
crosslinker concentration the swelling capacity decreases drastically. The effect of MBA crosslinker
concentration on the yield of poly(AMCASA) is

Figure 5. Influence of MBA concentration on yield of poly(AMCASA)

(S12).

Polym Int 50:946951 (2001)

Figure 6. Influence of APS concentration on water absorbency of

poly(AMCASA) (S12) in deionized water.

shown in Fig 5. As crosslinker concentration increases

the yield of the copolymer also increases due to the
increase in number of crosslinks.
Effect of initiator

The effect of initiator (APS) concentration on swelling

properties and polymerization rate of the copolymers
was also studied and the results are presented in Figs 6
and 7. The swelling ratio increases as APS concentration rises from 2.0  10 3 to 3.2  10 3 mol l 1 and
decreases slowly with further increase in concentration
of APS due to an increase in the number of radicals
produced as the concentration of APS increases. The
increase in the production of radicals at higher initiator
concentration increases the rate of polymerization,
thereby drastically lessening the crosslinking density,
and this is responsible for the decrease in the swelling
capacity of the copolymer.
Figure 8 shows the effect of NaCl concentration on
water absorbency of the copolymer. As NaCl concentration increases the absorbency decreases. It is
important to know the absorbency behaviour in salt
solutions.

Figure 7. Influence of APS concentration of polymerization time of

poly(AMCASA) (S12).

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K Mohana Raju, M Padmanabha Raju

Figure 10. Dry and swollen superaborbent copolymers (S12).

Figure 8. Influence of NaCl concentration on water absorbency (Q) of
poly(AMCASA) (S12) in deionized water.

The time required to reach the maximum swelling

capacity of the copolymers was studied and the results
are presented in Fig 9. The results indicate that the
SAPs absorb the maximum amount of water within
50 min. All the gels display good absorbency. The
photographs of dry and swollen SAPs are given in Fig
10.
Water retention of SAPs

One of the most important applications of SAPs is for

agricultural and horticultural purposes, especially for
effective utilization of water in dry and desert regions
and to transform them into `green and fertile lands'. In
this regard the preliminary testing of these SAPs for
water retention is carried out in small polyethylene
bags by growing the bean seeds (Dolichos) into plants
with and without using SAPs. Equal amounts of soil
(2 kg) were placed in two polyethylene bags; 0.5%
(w/w) of superabsorbent copolymer (S12) was thoroughly mixed with the soil in one of the bags (A). Ten
healthy seeds were placed in each of the two bags
together with 400 ml of water. Germination was
observed after 6 days in both bags. The growth pattern
of the plants was observed and care was taken to see

Figure 9. Swelling rate of poly(AMCASA) (S12).

950

that no pests and other diseases affected the plants.

There was little difference in the growth of the plants
in either bag for up to 15 days (Fig 11). However, after
15 days the plants in the bag containing untreated soil
(B) started wilting, whereas the plants in the bag
containing soil and SAP (A) were fresh. At this point
an additional amount (400 ml) of water was added to
the bag containing untreated soil (B). Even after 25
days of growth the plants in soil with SAP (A) were
fresh, whereas the plants in untreated soil (B) started
wilting despite the addition of another 400 ml of water
to the bag. After 40 days the plants wilted in both bags,
when an equal amount of water (400 ml) was added to
each. Thus by using these SAPs the moisture can be
retained in the soil for up to one month (Fig 12). The
plants in soil with SAP (A) were sustained for up to
one month without the addition of any more water.
Thus SAPs have good water retention capacity in soil.
The water that can be saved by using SAPs was 800 ml

Figure 11. Use of poly(AMCASA) as a soil conditioner for bean

(Dolichos) plant growth: (A) soil with 0.4% S12 based on soil weight; (B) soil
only. The plants are shown after 15 days.

Polym Int 50:946951 (2001)

Novel superabsorbing copolymers

in agriculture, especially in drought-prone areas where

the availability of water is insufcient.

ACKNOWLEDGEMENTS

The authors thank the UGC, New Delhi for nancial

support and sanction of the major research project
(sanction no (F.14-15/97 SR-1) dated 7/7/97) and Mr
P Ravi Senkar Reddy, Dr K Vani Naveen, ABR
Organics Limited, Hyderabad, for recording the IR
spectra of the samples.

REFERENCES

Figure 12. See legend to Fig 11: the plants are shown after 40 days.

(50%) up to 40 days. From this study it can be inferred

that water can be saved and managed in dry and desert
regions so that they can be used for the growth of
plants.
CONCLUSIONS

A number of novel superabsorbent copolymers were

synthesized in an aqueous solution by copolymerization of acrylamide, calcium acrylate and sodium
acrylate with N,N-methylenebisacrylamide, ethylene
glycol dimethacrylate and diallyl phthalate as crosslinking agents and ammonium persulfate as initiator.
The water absorbency of the copolymers is at a
maximum when MBA is used as crosslinking agent.
The synthetic variables (monomer feed ratios, MBA
concentration and initiator concentration) were also
studied. The copolymers were characterized by IR
spectroscopy. The absorbency of the SAPs was
measured in water and NaCl solutions; sample S12
had the highest water absorbency (Qmax = 384 gH2O
per g of gel). These SAPs have fast swelling capacity.
The water retention of soil is also enhanced by using
the above SAPs, and the growth of bean plants was
studied with and without adding SAPs to the soil. The
results of the present work indicate that SAPs have
good water retention capacity and will nd application

Polym Int 50:946951 (2001)

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