J Polym Environ (2013) 21:359–365
DOI 10.1007/s10924-012-0473-y
ORIGINAL PAPER
Synthesis and Characterization of Biodegradable
Starch-Polyacrylamide Graft Copolymers Using
Starches with Different Microstructures
Wei Zou • Xingxun Liu • Long Yu •
Dongling Qiao • Ling Chen • Hongsheng Liu •
Nuozi Zhang
Published online: 7 June 2012
 Springer Science+Business Media, LLC 2012
Abstract The effects of starch structures, in particular
amylose content, on grafting reactions were investigated
using thermal gravimetric analysis (TGA), nuclear mag-
netic resonance, X-ray diffraction (XRD). As a model
system, corn starches with different amylose contents (0,
26, 50 and 80 %) were grafted onto acrylamide to produce
superabsorbent polymers (SAPs). The weight loss mea-
sured by TGA at different temperature was used to analyze
the grafting ratio in quantity. In general, the grafting ratio
increased (about 10 %) with increasing starch amylose
content, and graft chain segment lengths were much lower
for the amylopectin-rich (waxy) starch. The high molecular
weight and branched structure of the amylopectin reduced
the mobility of the polymer chains and increased viscosity,
which resulted in resistance to chain growth. The water
absorption capability was increased with increasing amy-
lose content for the starch-based SAPs. XRD detection
showed that the crystalline structure of all starches was
destroyed after grafting reactions. The thermal stability of
the polyacrylamide grafted onto the starches increased by
about 10 C, which could be explained by the strong
bonding between the grafted polymer chains and the starch
matrices.
W. Zou  X. Liu  L. Yu  D. Qiao  L. Chen  H. Liu
Centre for Polymers from Renewable Resources, ERCPSP,
South China University of Technology, Guangzhou 510640,
China
L. Yu (&)  N. Zhang
CSIRO Materials Science and Engineering, Private Bag 33,
Clayton, VIC 3169, Australia
e-mail: long.yu@csiro.au
Keywords Starch  Amylose  Superabsorbent polymer 
Miscrostructure  TGA
Introduction
Superabsorbent polymers (SAPs) have been widely used
for hygienic applications, in particular in disposable dia-
pers and napkins, in which they capture secreted fluids such
as urine and blood. In addition, agricultural grades of SAPs
have been used in granular form to retain soil moisture in
arid areas. Now, due to environmental concerns, biode-
gradable SAPs are attracting increasing attention [1, 2],
particularly for agricultural applications. The biodegrad-
able properties of SAPs rely on the starch backbone [1–4].
Of the various starches that have been used as base mate-
rials to develop biodegradable starch-based SAPs, potato
[5–7], sago [8], cassava [9], and corn starch and its
derivatives [10–20] are the most popular.
One of the key characteristics of starches from different
resources is their amylose/amylopectin content. Essen-
tially, amylose has a linear structure of a-1,4 linked glucose
units, which makes it behave in a similar manner to con-
ventional synthetic polymers. The molecular weight of
amylose is about 9106, which is 10 times higher than that
of conventional synthetic polymers. Amylopectin, on the
other hand, has a highly branched structure of short a-1,4
chains linked by a-1,6 bonds, and its molecular weight is
about 9108, which is much higher than that of amylose.
The high molecular weight and branched structure of
amylopectin reduce the mobility of the polymer chains, and
interfere with any tendency for them to become oriented
closely enough to allow significant levels of hydrogen
bonding.
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High amylose maize starch [21] and high amylopectin
waxy cornstarch [22] have previously been used to produce
starch-based SAPs. Comer and Jessop [23] compared two
types of starch (high amylose and high amylopectin) and
found no significant difference in the grafting efficiency of
starch-g-poly (methyl methacrylate) prepared by emulsion
photopolymerization. However, the differences in the
grafting efficiency of high amylase and high amylopectiun
starches with acrylamide have recently been observed [24].
The aim of this work is to investigate the effect of starch
structures on chemical modifications, with a focus on the
effects of amylose on the grafting reactions, microstruc-
tures and performance of the starch-based SAPs. Grafting
acrylamide onto corn starches with different amylose
contents to produce SAPs was used as a model system in
this work. The weight loss measured by TGA at different
temperature was used to analyze the grafting ratio in
quantity. The thermal stability of the grafted groups and the
starches after grafting were also investigated.
Experimental
Materials
Commercially available corn starches (from Penford,
Australia) with different amylose contents were used in this
work (Table 1). All other chemicals used are also com-
mercially available and were supplied by Huagong
Chemicals (China) at the chemically pure grade.
Preparation of Starch-Based SAPs
The SAPs from different starches were prepared under the
same conditions, as follows:
• 5.00 g of starch in distilled water (80 mL) was firstly
gelatinized at 121 C for 15 min. Then 0.50 g of ceric
ammonium nitrate (CAN) was added into the gelati-
nized starch solution at 60 C to react for 10 min in a
nitrogen atmosphere.
• A solution of acrylamide (AM) (15.00 g) containing
N,N0 -methylene-bisacrylamide (N-MBA) (0.07 g) was
added into the gelatinized starch at 60 C to react for
Table 1 Details of starches used in the experiments
Starch Amylose Molecular Moisture
content (%) weight* (Mn) content (%)
Waxy 0 20,787,000 12.9
Maize 26 13,000,000 12.7
Gelose 50 (G50) 50 5,115,000 12.3
Gelose 80 (G80) 80 673,000 12.2
*Average number molecular weight measured by GPC provided by
Penford
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J Polym Environ (2013) 21:359–365
120 min. Then sodium hydroxide solution of NaOH
(6.84 g) in distilled water (125 mL) was added to the
flask at 90 C for 120 min.
• The modified starch was washed with distilled water to
a pH of 7 then rewashed with ethanol. The sol fraction
was removed during the water washing. The product
was dried to a constant weight in an oven at 90 C.
The method has been described in detail previously
[24–26].
The percentages of graft polymer, free polymer and sol-
uble starch were determined through separation by washing
using distilled water, and acid hydrolysis using HCl [1].
Characterization
Thermal Gravimetric Analysis (TGA)
A PerkinElmer Diamond TGA system was used to deter-
mine the grafting amount of the graft copolymer, based on
the identified decomposition temperatures of the starch and
grafted groups [1, 27, 28]. The thermal stability of the
grafted groups and the graft starches were investigated by
heating samples from 30 to 600 C at 10 C/min in a
nitrogen atmosphere. Water release rates were also mea-
sured by TGA through heating swollen samples at the
lower rate of 2 C/min.
Nuclear Magnetic Resonance (NMR)
A Varian NMR 300 system operating at a resonant fre-
quency of 75 MHz for 13C was used to study the graft
positions and graft ratios on specific carbons in the star-
ches. Solution 13C-NMR spectra were measured at room
temperature using a 10 mm solution probe-head via con-
ventional methods. Tetramethylsilane was used as an
internal reference to determine chemical shifts.
Water Absorption Capacity
Water absorption capacity of the polymer gels was measured
by immersing samples in distilled water for 24 h at ambient
temperature. Each swollen gel sample was passed through a
200-mesh screen to remove excess water, and then weighed.
X-ray Diffraction (XRD)
A Bruker D8 diffractometer (operating at 40 kV, and
40 mA, with Cu Ka radiation monochromatized with a
graphite sample monochromator, LynxExe array detector,
scanning speed of 17.7 s per step, and scanning step 0.02)
was used to study the crystalline structures of the starch
granules and starch-based SAPs.
J Polym Environ (2013) 21:359–365 361

Results and Discussion

TGA weight loss measurements were used to calculate

grafting characteristics, which are expressed as the per-
centage of add-on and the percentage of grafting ratio, as
reported previously [1]. In order to simplify the TGA
curves, all samples were pre-dried at 105 C under vacuum
conditions for 24 h so that weight loss due to moisture
evaporation could be discounted. The percentage weight
loss at the decomposition temperatures of a starch and
polyacrylamide (PAM) grafted onto the starch can be
determined in the TGA thermograms. Figure 1 presents the
TGA thermograms obtained in this work for a typical
sample of the dried waxy starch, as well as a waxy starch-
based SAP (SAP-waxy), both before and after acid
hydrolysis. The thermogravimetric (TG) curve for the
native starch (Fig. 1a) shows that significant weight loss
began at about 270 C. Correspondingly, there is a peak in
the derivative thermogravimetric (DTG) curve at about
310 C due to starch decomposition. Lower decomposition
temperatures were observed for the native starches with
higher amylose content [29–31].
Figure 1b shows that two degradation steps occurred for
the grafted starch, with the first peak P1 in the DTG curve at
about 290 C being assigned to starch decomposition after
graft modification. Correspondingly, D1 in the TG curve
represents the weight loss of the starch backbone. It should be
noted that the peaks of decomposition temperature for the
modified starches were lower than those for the native star-
ches (cf. Fig. 1a). A similar phenomenon has previously
been observed [1, 32, 33], and can be explained by the
destruction of the crystalline structure in the starch granules
during gelatinization and modification [34, 35]. The second
peak P2 at about 405 C is the thermogram of the acrylamide
in the starch-g-PAM. The weight loss D2 represents the
decomposition of the PAM grafted onto the starch.
The thermogram for the acid-hydrolyzed SAP-waxy
(Fig. 1c) also shows two decomposition stages. Apart from
the acrylamide decomposition peak P21 in the DTG curve at Fig. 1 TGA thermograms of: a dried waxy starch, b SAP-waxy, and
c acid-hydrolyzed SAP-waxy
about 395 C, a new peak P22 appears at about 230 C,
which is attributed to the decomposition of the side groups
computed from the weight difference between the grafted
and branches in the graft polymer [1]. Correspondingly, D21
PAM and the total polymers. The grafting ratio (GR) reveals
and D22 represent the weight loss of P21 and P22 respec-
the degree of PAM grafted onto the starch backbone [1, 36].
tively. No second peak was detected for the starch-g-PAM
AO and GR were calculated based on D1 and D2 respec-
(see Fig. 1b), since the PA chains grafted onto the starch
tively in Fig. 2b by:
were very short [20] and thus there were no side groups. P
The percentage weight loss detected by TG for starch and ðweight loss at D2 Þ  100
AOð%Þ ¼ P ð1Þ
starch-g-PAM (Fig. 1b) can be converted to the percentage ðweight loss at D1 and D2 Þ
of starch and PAM grafted onto the starch respectively, P
ðweight loss at D2 Þ  100
which can then be used to calculate the grafting character- GRð%Þ ¼ P ð2Þ
ðweight loss at D1 Þ
istics (expressed in terms of the percentages of add-on and
grafting ratio). The weight in percentage of PAM in the graft It can be seen in Fig. 2 that the TGA thermograms for the
polymer—or the so-called ‘‘percentage add-on’’ (AO)—was different starches and their corresponding starch-g-PAM

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Fig. 2 TGA thermograms of
starches and their corresponding
SAPs both before and after acid
hydrolysis: a waxy, b maize,
c G50, and d G80
both before and after acid hydrolysis exhibit similar pat-
terns. The results listed in Table 2 show that the high
amylopectin starch (SAP-waxy) recorded the lowest AO
and GR values. The lower reaction efficiency could be
because the double-helix crystalline structures formed by
amylopectin’s short branched polymer chains are less
flexible than the long chains in amylose. It should be noted,
however, that the highest amylose starch (SAP-G80) did
not record the highest AO and GR. This phenomenon could
be due to the fact that the G80 has high and multiple
gelatinization temperatures [37], so that it may not have
been fully gelatinized during the first stage of the grafting
reaction. This issue will be investigated in future work.
The decomposition temperature and the percentage
weight loss at different temperatures were also used to
investigate the thermal stability of the starches and the
groups grafted onto them. It has been noted that the thermal
stability of PAM grafted onto starch (P2 in SAPs) was
higher than that of the ungrafted polymer (P21 in acid-
hydrolyzed SAPs). For example, the decomposition tem-
peratures of P2 and P21 were 405 and 395 C respectively
for SAP-waxy (see Fig 1b, c). This could be explained by
the strong bonding between the grafted polymer chains and
the starch matrix in the graft polymer, and imidization [1].
There was no observable difference in the decomposition
temperature of the PAM grafted onto the different starches.
Graft positions and graft ratios on specific carbons in
the starches was investigated by NMR. As the 13C-NMR
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J Polym Environ (2013) 21:359–365
spectra of PAM and starch-g-PAM have been widely
reported previously [38–40], this work focused on the
carbons in starches. The only observable difference in the
peaks for the carbon atoms was a new peak detected at
d = 61.8 ppm for the starch-based SAPs, which is close to
the peak for C6 at d = 63.5 ppm (see Fig. 3). This result,
which is similar to that previously reported [24, 41], indi-
cates that the hydroxyl groups of C6 participated mainly in
the graft reaction. The ratio of the peaks at d = 63.5 and
61.8 ppm were used to determine the ratio of C6-AM
grafting. Table 2 shows the composition of the different
SAPs, in which ‘‘Add-on (%)’’ represents the PAM seg-
ments in a sample, and ‘‘Reaction ratio of C6’’ represents
the number ratio of C6 linked to the PAM. All SAP sam-
ples contained 70–80 wt% of PAM segments in the grafted
starch. It has been noted that the sample based on waxy
starch had 53.2 % of C6 involved in the grafting reactions,
which was significantly higher than other starch-based
SAPs (19–22 %). As grafting occurred mainly on C6, the
length of the grafted PAM segments in each grafted starch
was calculated based on the mole mass of glucose (160)
and AM (71), and the results are also shown in Table 2.
The results show that the segment length for the SAP-waxy
was much shorter (3.0) than other starch-based SAPs
(ranged from 8.2 to 9.5). This would indicate that the high
molecular weight and branched structure of amylopectin
reduced the mobility of the polymer chains, resulting in a
higher viscosity and resistance to chain growth. The add-on
J Polym Environ (2013) 21:359–365 363

Table 2 Graft reactions,

Samples Grafting reaction Reaction ratio PAA segment Water viscosity Water
composition and properties of
of C6 (%) length (no.) (10 rad/s) (Pa.s) absorption (%)
the starched-based SAPs Add-on Grafting
(%) ratio (%)

SAP-waxy 41.29 70.34 53.2 3.0 268 320 ± 57

SAP-maize 44.07 78.79 21.6 8.2 185 286 ± 36
SAP-G50 43.45 76.84 18.3 9.5 105 523 ± 44
SAP-G80 42.77 74.72 20.1 8.4 123 724 ± 68

starch may have also contributed to the higher water

Fig. 3 13C-NMR spectra of native starch (maize) and the starch-
based SAPs
absorption. An earlier study by Michaels [42] showed that
PAM with longer chains was more effective in the floc-
culation of suspensions, and a similar phenomenon has also
been observed for graft copolymers of PAM on starches
[39, 43–45]. The rigid and branched structure of amylo-
pectin hinders water movement in the gel, which results in
lower water absorption. The shorter grafted chains of high
amylopectin starch, as detected by NMR, also correspond
with the observed water absorption behaviour.
Figure 4 shows the water release rates during heating, as
measured by TGA and, as expected, water evaporated
during heating. As there was no significant difference in the
release rates of the different SAPs, it would appear that the
length of the grafted AM chains has not changed the nature
of the bond between the AM and water.
The XRD spectra for the different native starches and
their corresponding SAPs are shown in Fig. 5. The spectra
for the native waxy and maize starches (high amylopectin
content) exhibited a typical A-type pattern, while those for
the G50 and G80 starches (high amylose content) exhibited
a strong B-type pattern. Overall, an increase in amylose
content in the native starches led to a progressively weaker
scanning intensity, except for the peaks observed at around
2h = 18, which is a characteristic of V-type starches.
These results are similar to those previously reported
[46–48]. In the spectra for the various SAPs, the weak but

and graft ratio were also calculated by the gravimetric

method [1, 24] based on the percentages of graft polymer,
free polymer and soluble starch determined through sepa-
ration by washing using distilled water, and acid hydrolysis
using HCl.
Table 2 also gives the results of water absorption
capacity of the SAPs from different starches. It can be seen
that the SAPs from amylase-rich starches generally had a
higher capacity, which corresponds with the percentages of
AO and GR. The high molecular weight and branched
structure of amylopectin reduced the mobility of the
polymer chains, and interfered with any tendency for them
to become oriented closely enough to permit significant
levels of hydrogen bonding. Furthermore, based on the
NMR results, the longer grafted segments in high amylose Fig. 4 Water release rates of SAPs during heating at 2 C/min

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Fig. 5 XRD spectra of native starches and their corresponding SAPs
sharp peaks at around 2h = 30 could be residual PAM
that was not totally removed by washing.
Conclusions
Corn starches with different amylose/amylopectin contents
(0, 26, 50 and 80 %) were grafted with acrylamide, for use
as a model system to study the effects of starch micro-
structures on starch modification. The results showed that,
in general, the grafting ratio was increased (about 10 %)
with increasing amylose content, and the graft chain seg-
ment length was much lower for the SAPs based on the
high amylopectin (waxy) starch.
In generally, the water absorption capability of the
starch-based SAPs increased with increasing amylose
content, which corresponds with the graft ratio and relates
to the segment length of the polyacrylamide grafted onto
the starches. The high molecular weight and branched
structure of amylopectin reduced the mobility of the
polymer chains, resulting in higher viscosity and resistance
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J Polym Environ (2013) 21:359–365
to chain growth. There was no significant difference in the
water release rates of the different SAPs, which indicates
that the length of grafted acrylamide chains did not change
the nature of the bond between the acrylamide and water.
XRD detection revealed that the crystalline structure of
all starches were destroyed by the graft reactions. The
thermal stability of the polyacrylamide grafted onto the
starches was increased by about 10 C, which could be
explained by the strong bonding between the grafted
polymer chains and the starch matrices.
Acknowledgments The authors from SCUT, China, would like to
acknowledge the research funds NFSC (21174043, 31130042),
RFDPHE (20110172110027) and FRFCU (2012ZZ0085). Thanks
also to Dr S. Li (CSIRO) for contact angle measurements and
analysis.
References
1. Lanthong P, Nuisin R, Kiatkamjornwong S (2006) Carbohydr
Polym 66:229
2. Zohuriaan MJ, Kabiri K (2008) Iran Polym J 17:451
3. Arvanitoyannis I (1999) J. Macromol Sci Rev Macromol Chem
Phys C39:205
4. Psomiadou E, Arvanitoyannis I, Biliaderis CG, Ogawa H,
Kawasaki N (1997) Carbohydr Polym 33:227
5. Zhang LM, Chen DQ (2001) Starch-Stärke 53:311
6. Zhang LM, Hu ZH (2002) Starch-Stärke 54:290
7. Shaikh MM, Lonikar SV (2009) J Appl Polym Sci 114:2893
8. Han TL, Kumar RN, Rozman HD, Noor MAM (2003) Carbohydr
Polym 54:509
9. Nakason C, Wohmang T, Kaesaman A, Kiatkamjornwong S
(2010) Carbohydr Polym 81:348
10. Cho CG, Lee K (2002) Carbohydr Polym 48:125
11. Song H, Zhang SF, Ma XC, Wang DZ, Yang JZ (2007) Carbo-
hydr Polym 69:189
12. Fanta GF, Felker FC, Shogren RL (2004) Carbohydr Polym 56:77
13. Ma YHC, Manolache S, Sarmadi M, Denes FS (2004) Starch-
Stärke 56:47
14. Samaha SH, Nasr HE, Hebeish A (2005) J Polym Res 12:343
15. Xu SM, Wei J, Feng S, Wang JD, Li XS (2004) J Polym
ResTaiwan 1(1):211
16. Xu S, Wang J, Wu R, Wang J (2006) Carbohydr Polym 66:55
17. Meshram MW, Patil VV, Mhaske ST, Thorat BN (2009)
Carbohydr Polym 75:71
18. Mostafa KM, Morsy MS (2004) Starch-Stärke 56:254
19. Kaith BS, Jindal R, Jana AK, Maiti M (2010) Bioresour Technol
101:6843
20. Salam A, Pawlak JJ, Venditti RA, Ei-tahlawy K (2010)
Biomacromolecules 11:1453
21. Yamaguchi M, Watamoto H, Sakamoto M (1988) Carbohydr
Polym 9:15
22. De Bruyn H, Sprong E, Gaborieau M, Roper JA, Gilbert RG
(2007) J Polym Sci Pol Chem 44:4185
23. Comer CM, Jessop JLR (2008) Starch-Stärke 60:335
24. Zou W, Yu L, Liu X, Qiao DL, Zhang X, Chen L, Zhang R
(2012) Carbohydr Polym 87:1583
25. Meister JJ (1981) J Rheol 25:487
26. Wu J, Lin J, Zhou M, Wei C (2000) Macromol Rapid Commun
21:1032
27. McNeill IC, Sadeghi SMT (1990) Polym Degrad Stab 29:233
J Polym Environ (2013) 21:359–365
28. Athawale VD, Lele V (2000) Starch-Stärke 52:205
29. Liu X, Yu L, Xie F, Li M, Chen L, Li X (2010) Starch-Stärke
62:139
30. Liu X, Yu L, Liu H, Chen L, Li L (2009) Cereal Chem 86:383
31. Soares RMD, Lima AMF, Oliveira RVB, Pires ATN, Soldi V
(2005) Polym Degrad Stab 90:449
32. Zhang X, Golding J, Burgar I (2002) Polymer 43:5791
33. Beninca C, Demiate IM, Lacerda LG, Carvalho Filho MAS,
Ionashiro M, Schnitzler E (2008) Eclet Quı́m São Paulo 33:13
34. Fares MM, Ei-faqeeh AS, Osman ME (2003) J Polym Res
Taiwan 10:119
35. Athawale VD, Lele V (1998) Carbohydr Polym 35:21
36. Athawale VD, Rathi SC (1999) J Macromol Sci Rev Macromol
Chem Phys C39:445
37. Liu H, Yu L, Xie W, Chen L (2006) Carbohydr Polym 65:357
365
38. Gurruchaga M, Goni I, Vazquez B, Valero M, Guzman GM
(1992) Macromolecules 25:3009
39. Pal S, Nasim T, Patra A, Ghosh S, Panda AB (2010) Int J Biol
Macromol 47:623
40. Sen G, Kumar R, Ghosh S, Pal S (2009) Carbohydr Polym 77:822
41. Zhang Q, Xu K, Wang P (2008) Fibers Polym 9:271
42. Michaels AS (1954) Ind Eng Chem 46:1485
43. Ghosh S, Sen G, Jha U, Pal S (2010) Bioresour Technol 101:9638
44. Rath SK, Singh RP (1997) J Appl Polym Sci 66:1721
45. Rath SK, Singh RP (1998) J Appl Polym Sci 70:1795
46. Douzals JP, Marechal PA, Coquille JC, Gervais P (1996) J Agric
Food Chem 44:1403
47. Cheetham NWH, Tao LP (1998) Carbohydr Polym 36:277
48. Liu H, Yu L, Simon G, Dean K, Chen L (2009) Carbohydr Polym
77:662
123