International Journal of Agriculture Innovations and Research

Volume 6, Issue 1, ISSN (Online) 2319-1473

Manuscript Processing Details (dd/mm/yyyy) :
Received : 23/06/2017 | Accepted on : 01/07/2017 | Published : 10/07/2017

Synthesis of the Swelling Polymers based on Cellulose

Grafted with Acrylic Monomers and Survey on
Mustard Greens
Nguyen Thi Hong Hanh
Department of Chemistry, Faculty of Environment, Vietnam National University of Agriculture.

Abstract – Acrylic acid (AA) were grafted polymerized cellophane and rayon. Converting cellulose from energy
onto cellulose. Acrylic groups were introduced onto cellulose crops into biofuels such as cellulosic ethanol is under
backbone by a homogeneous synthesis. This reaction was investigation as an alternative fuel source. Cellulose has
carried out in aqueous solution using ammonium per sulfate no taste, is odourless, is hydrophilic with the contact angle
(APS) as an initiator and Methylene Bis Acrylamide (MBA)
of 20–30o, is insoluble in water and most organic solvents,
as a crosslink agent. Infrared spectroscopy (FT-IR) was
carryout to confirm the chemical structure of swelling is chiral and is biodegradable. It can be broken down
polymer. Moreover, morphology of samples was examined by chemically into its glucose units by treating it with
scanning electron microscopy (SEM). The element concentrated acids at high temperature [2].
composition of polymer was determined by energy dispersive Cellulose is one of the inexpensive, biodegradable,
analysis of X-rays (EDX). Their equilibrium swelling degree renewable and the most abundant organic raw material and
was evaluated in various conditions by tea-bag method. The it has been widely studied during the past decades.
results showed that the maximum swelling of polymer is Cellulose lacks some properties that synthetic polymers
about 250 grams per gram in distilled water. Initial have in some applications although it has many useful
experiment on mustard green, this material has the ability to
properties. Modification of cellulose by graft
moisturize and provide nutrients for plants, as demonstrated
by the rate of germination, plant height, and leaf area in the copolymerization provides a significant route to alter the
CT2, CT3 with additional 3% and 5% swelling polymers physical and chemical properties of cellulose materials.
were both higher than CT1 – the control formula. The leaf Cellulose has been graft polymerized using various
area in CT1, CT2, CT3 arranged in turn were 115,37cm2, techniques. Most of them are based on a grafting-from
180,69cm2, 187,51cm2 respectively. This swelling polymers process, where radical is formed along polymer backbone
can be used as a moisturizer and keep water for trees. either by various chemical initiators or by irradiation, and
then, the free radical polymerization of vinyl monomers
Keywords – Cellulose, Swelling, Polymer, Crosslink, occurs [3, 4, 5, 6]. In these methods, chain scission can
Acrylic Acid, Mustard Greens.
occur and cellulose backbone is not kept intact to form the
flexible circuits and then to form swelling polymer. Super
I. INTRODUCTION absorbents are widely used in many products such as in
disposable diapers, feminine napkins, soil for agriculture
Cellulose is an organic compound with the formula and horticulture, gel actuators, water blocking tapes,
(C6H10O5)n, a polysaccharide consisting of a linear chain medicine for the drug delivery systems and absorbent pads
of several hundred to over ten thousand β(1→4) linked D- where water absorbency or water retention is important [3,
glucose units. Cellulose is the structural component of the 7, 8, 9].
primary cell wall of green plants. Cellulose is the most
common organic compound on Earth. About 33% of all
II. MATERIALS AND METHODS
plant matter is cellulose, the cellulose content of cotton is
90% and that of wood is 40–50% [1, 2].
A. Synthesis of Swelling Polymer
The swelling polymer was synthesis from rice husk: 5g
cellulose from rice husk was finely ground and the
distilled water was charged. This mixture is stirred for 15
min until a clear solution is obtained. The reactor was
immersed in a thermostated at 80oC. Then, 2.75ml acrylic
acid and 0.01g methylene bis acrylamide were added and
stirred for 15 min. After that, 0.05g ammonium per sulfate
was added, stirred for 10-15 min obtained gel. Cooled at
room temperature and poured to excess non-solvent
Fig. 1. The structure of cellulose acetone and remained for 6h to dewater. Then, acetone
was decanted and the product was cut into small pieces
For industrial use, cellulose is mainly obtained from (diameter  5mm). Again, the fresh acetone was added and
wood pulp and cotton. It is mainly used to produce remained for 24h. The filtered gel was dried at 45 oC for
paperboard and paper; to a smaller extent it is converted 6h. After grinding, the powdered polymer was stored away
into a wide variety of derivative products such as from moisture and heat.
Copyright © 2017 IJAIR, All right reserved
33
 International Journal of Agriculture Innovations and Research
Volume 6, Issue 1, ISSN (Online) 2319-1473

B. Characterization of Swelling Polymer

The structure of swelling polymer was analyzed by the
following modern methods: Infrared spectroscopy (FT-IR)
was obtained by Nicolet Magna 550, the samples
powdered were prepared in KBr pellets. X-ray diffraction
(XRD) technique using a Bruker B8 Advance X-ray
powder diffractometer. The elemental composition was
determined by Energy dispersive analysis of X-rays (EDX,
Varian Vista Ax). The size and morphology of materials
was examined using scanning electron microscopy (SEM,
Hitachi S-4800FEG) Fig. 2. FT-IR spectrum for swelling polymer
C. Measurement of Swelling Ratio (SR)
The swelling polymers (Wo, g), which was put into a In this Figure, a bands appear in the IR spectrum that
tea-bag of nonwoven fabric, was immersed in water for could indicate a polymer degradation process. The
24h. The treated bag was allowed to hang on a holder for increase of the band at 3446cm-1 signals a vibration of –
10 min to separate the swollen sample (Ws, g) from the OH groups. The increase of the band 2952 cm-1 signals a
unabsorbed water (Feng Hua, 2001). Degree of swelling vibration of the C-H stretching of new methylene groups
ratio was defined as follows: in the polymeric unit. The pick at 1669 cm-1 is due to the
SR (g/g) = (Ws-Wo)/ Wo >C=O bending. The pick at 1450cm-1 is due to the –CH2-
Influence of pH on the swelling behavior of the swelling bending. The band at 1329 cm-1 corresponds to a vibration
polymers was studied. Monitor the polymer’s ability to of C-O stretching The peaks in the region from 1174-861
release water under dry conditions in air cm-1 are due to –C-O- stretching, the –C-O-C- pyranose
D. Survey the Moisture Rention of the Swelling ring skeletal vibration gives a prominent band at 1054cm-1
and the –CH2– rocking vibration at 786cm-1 corresponds to
Polymer on Mustard Green
the methylene groups. Accordingly, the garft reaction was
The experiment was conducted in greenhouse, covered
occurred.
roof, planted in pots. Each pots was germinated 3 seeds,
In the Fig. 3a, all the samples exhibit typical cellulose
watered fully, trimmed excess leaves only 1 plant per pot
after germination. The experiments were arranged in diffraction angles (2) around 15o, 16o and 22o. In the Fig.
complete randomized block, each formula (CT) was 3 3b, these vertices still remain but not clear, suggesting that
times repeated, each replicate has 30 trees. Fixed the the crystal phase in the cellulose has decreased. That
amount of 300g of potting media and fertilizer are the mean, the grafting reaction have been formed.
same for each of the experiments. The amount of irrigation
water in CT2 and CT3 were 20% decreased compared to
CT1.
CT1: Alluvial soil: Rice husk char (2: 1).
CT2: 97% [Alluvial soil: Rice husk char (2: 1)] + 3%
swelling polymers.
CT3: 95% [Alluvial soil: Rice husk char (2: 1)] + 5%
swelling polymers.
Monitoring of indicators: Germination percentage (%)
was statistic at 10 days after sowing. Plant height (cm),
leaf area (cm2), water content in media (g), water content
in tree (%) was measured at 40 days after sowing. After 40
days sowing, stop watering and monitor the amount of
water in the tree
E. Methods of Data Analysis and Processing
The data was processed by biological statistical method
using IRRISTAT and excel software.

III. RESULTS AND DISCUSSION

A. Characterization of Swelling Polymer

The FT-IR method allows for identifying some
information of the material structure. The FT-IR method is
Fig. 3. XRD patterns of cellulose (a) and polymer (b)
based on the interaction of light in the infrared region with
the bonds in the sample. The light with the certain
The EDX method allows to determine the composition
wavelength will vibrate certain links. So that energy
of elements in the materials. In EDX spectrum of the
absorption is closely related to the molecular structure
sweeling polymers (Fig. 4), the swelling polymer which
prepared from rice husk material has high carbon
Copyright © 2017 IJAIR, All right reserved
34
 International Journal of Agriculture Innovations and Research
Volume 6, Issue 1, ISSN (Online) 2319-1473

compounds, with amount of carbon about 40.68%. This is B. The Swelling Ratio of Polymer
a short change cellulose component, which is the source of The swelling ratio of polymer in distilled water: The
organic nutrients for plant growth. In addition, the swelling polymers was synthesize on the copolymerization
composition also contains some other elements Si reaction by the grafting of acrylic acid onto the cellulose.
(8.03%), N (0.20%), P (0.06%), K (0.27%), Zn (0, 11%),
Fe (0.04%).... These are micronutrients essential for plant

Fig. 4. EDX spectrum of swelling polymers

The SEM micropraphs of the husk shows that the husk

has a fibrous structure, characteristic for cellulosic fibers.
Cellulose is a carbohydrate compounds, made from
hundreds, thousands of β-D-Glucose units, forming
straight chains. The hydrogen atom on this circuit forms a
hydrogen bond with the oxygen atom on the adjacent
chain, keeping the cellulose bonds tightly bonded to each
other, thus creating a strong network structure. So that,
Fig. 6. The swelling of polymers
rice husk only capable of absorbing moisture due to
interaction with water, unable to swell to keep large
The product has hight moisturizing capacity, maximum
amounts of water
swelling polymer in distilled water is about 250 gram per
Swelling polymer are synthesized from finely grated
gram polymer (Fig.6). Thus, this synthetic products that
rice husks. With a short chain, flexible cellulose circuit,
have hight water retention, It ability can be used to store
combined with bridges of acrylic acid, MBA between the
and regulate water for crops, especially in drought areas
vessels, makes the product a spatial, spatial structure that
and lack of water.
stores a large amount of water
The mechanism of water absorption of synthesis
polymers was explained by the fact that polymer chains
containing some functional groups -COOH and -OH are
present in the structure of acrylic acid and cellulose. The -
COOH, -OH groups are hydrophilic, so when introduced
into the water, there is a hydration interaction between the
functional groups on the polymer and the solvent. These
effects reduce energy and increase the entropy of the
system. Because of the hydrophilic nature, polymer chains
tend to disperse indefinitely in water, which also increases
entropy. The presence of mesh material forming a three-
dimensional space network, the elastic force of the
polymer network blocking the unlimited dissolved. In the
system, there exists a balance between the network
elasticity and the unconfirmed trend of the circuit. For
ionic polymers, neutralized circuits contain the same
charge. The charge neutralization is maintained when the
negatively charged –COO- groups are balanced with
positively charged Na+ ions. When exposed to water, Na+
ions are hydrated to reduce their gravitational pull on the -
COO- groups (due to high dielectric constant of water).
This process allows free Na+ ions to move freely within
the network to form osmotic pressure inside the gel.
However, the Na+ ions are flexible but cannot move away
Fig. 5. SEM micropraphs of polymer: (a) rice husk, (b) from the gel because they are still weakly absorbed by the
polymer -COO- groups along the polymer main chain and
Copyright © 2017 IJAIR, All right reserved
35
 International Journal of Agriculture Innovations and Research
Volume 6, Issue 1, ISSN (Online) 2319-1473

resembles being trapped by a semi-permeable membrane. At pH = 10-11, the higher concentration of cation (Na+)
Therefore, the dynamic force of the process is the will restrain the extending of the polymer networks,
difference in osmotic pressure inside and outside the gel therefore the swelling of the polymer is inhibited.
[3, 8]. The water release capability of swelling polymer (Fig.
Effect of pH on the swelling ratio of the swelling 8): Take 1 gram swelling polymer after absorbing water,
polymers (Fig. 7): When the polymers are immersed in to dry naturally in air. The amount of water absorbed in
buffer solutions with low pH (pH = 3-4), the ionization of the polymer decreases in time, maintaining good humidity
the carboxylic acid groups is very low, and the for about 30 days. After about 80 days, the amount of
electrostatic repulsion between the ionized groups in the water in the sample remain about 6 grams per gram
networks has hardly any contribution to the swelling of the sample. Thus, this swelling polymer is able to retain water
hydrogels. This leads to a collapsed polymer network with and gradually release water for tree to used
a rather limited SR. A transition of the SR can be observed
between pH 5 and pH 6, at this pH range, dissociation of
the carboxylic acid groups occurs. Both the charge
repulsion and the presence of free counter-ions in the gel,
which cause a high osmotic pressure, contribute to the
improved SR. [7].
At pH = 7- 9, the SR of the polymers is almost constant
and maximum 252g/g because of the charge repulsion and
elastic stress of the hydrogel networks. In alkaline buffer
solutions, the carboxylic acid groups become Fig. 8. The water release capability of swelling polymer
progressively ionized. Therefore, the swelling polymers Survey the moisture retention of the swelling polymer on
more rapidly because of a large swelling force created by mustard green
the electrostatic repulsion between the ionized groups in
the network. The use of humectants in agriculture has been a
technological advance applied in many countries around
the world since the 1980s. The effectiveness of this
measure has been confirmed in the United States, Canada
and China. …. with the renovations of the desert, the
greening of barren hills in the United States, the
application of Brazilian coffee fields, and sugar beets in
Germany ... the results show that they are increased crop
yields, reduced plant mortality, reducing the necessary
care for plants, saving time and watering [8].
In this study, we were studied the effect of this polymers
Fig. 7. Effect of pH on the swelling behavior of the
was synthesized from rice husks with acrylic acid on the
swelling polymers
growth and development on mustard gree.

Table 1. The moisture retention of the swelling polymer on mustard green

CT Seed Plant Canopy Number of Leaf area Water Water
germination height diameter leaf (cm2) concentration in concentration in
(%) (cm) (cm) (leaf/tree) potting media (g) leaf (%)
CT1 78.22 17.32 17.02 6.62 115.37 77.53 93.03
CT2 90.16 20.44 19.78 6.91 180.69 118.24 93.32
CT3 93.87 21.87 22.14 7.05 187.51 143.81 93.35
LSD (5%) 1.83 1.06 0.44 0.84 13.08 7.84 0.98
CV % 4.01 2.20 1.96 3.75 5.37 3.13 2.10

The results showed that in CT2 and CT3, when adding Although CT2, and CT3 had an irrigation water content of
3% and 5% swelling polymer, the rate of seed germination 20% lower than CT1, the water content in potting media
increased 11.94 to 16.56% compared to CT1. After 40 was always higher than 152.51% (CT2) and 185.49%
days sowing, the plant height and leaf area of CT2, CT3 (CT3) compared to CT1. And water content in the leaf
were both higher than CT1- the control formula. In turns, remained stable at 93.03-93.35% in accordance with
the plant heigh increase 18.63- 26, 27%, the leaf area Ministry of Health – Institute of Nutrition studies [10]
increase 56,62- 62,53% In addition, the swelling polymer is made from rice
This can be explained in CT2 and CT3 by the addition husk, this material provides a large of organic
amount of swelling polymer, which is capable of good components, micronutrients in the rice husks, increasing
moisture retention, providing adequate moisture for seed the organic nutrients content, then that make the plants
germination. This is shown by analyzing the water content development better. This product has been researched and
in the potting media and the water concentration in leaf. tested by author and partners. It has good results. Nguyen

Copyright © 2017 IJAIR, All right reserved

36
 International Journal of Agriculture Innovations and Research
Volume 6, Issue 1, ISSN (Online) 2319-1473

the Hung shows that potting media has 25% moisturizing REFERENCES
agent by volume which is suitable for spinach and the
potting media has 20% moisturizing agent by volume [1] Aida Neira, Miguel zarraga, Rosa catalan (2008), Degradation of
which is suitable for celery [11]. Nguyen Thi Hong Hanh acrylic acid – grafted cellulose in aqueous medium with radical
initiators, J. Chil. Chem. Soc., Vol 53, No 1, pp. 1410-1414.
experimented in mustard green, the results show that the
[2] Ming-Guo Ma, Jie-Fang Zhu, Ning Jia (2010), Rapid microware-
treatment with additional 5% of moisturizing polymes by assisted synthesis and characterization of cellulose -
weight that has the rate of germination 91.11%, more than hydroxyapatite nanocomposites in N,N-dimethylacetamide
13.7% compare with the control treatment and the yield solvent, Carbohydrate research, Vol. 345, pp. 1046-1050.
[3] A. Pourjavadi, A. M. Harzandi, H. Hosseinzadeh (2004),
reached were about 61.41 g/plant. It was larger than the
Modified carrageenan 3. Synthesis of a novel polysacch aride-
control treatment were 33.01 g/plant [12] based superabsorbent hydrogel via graft copolymerization of
Survey the water retention capacity on conditional lack acrylic acid onto kappa-carrageenan in air, European polymer
of water (Fig.9) The result show that: In CT1- the control Journal, Vol. 40, pp. 1363-1370.
[4] Elisabetta Princi, Silvia Vicini, Enrico Pedemonte, Alessandro
media, without swelling polymer, water content in the tree
Mulas, Enrico Franceschi, Giorgio Luciano, Vincenzo Trefiletti
decreases from 98.42% at 0 day to 37.26% at 7 days and (2005), Thermal analysis and characterisation of cellulose
22.18% at 14 days stopped watering. In the CT2 and CT3, grafted with acrylic monomers, Thermochimica Acta, Vol. 425,
with present of the swelling polymer, water content in the pp. 173-179
[5] R.O.Mazzei, E. Smolko, A. Torres, D. Tadey, C. Rocco, L.
tree decreases slowly. This swelling polymer can be retain
Gizzi, S. Strangis (2002), Radiation grafting studies off acrylic
water ad release them for tree to used so that can acid onto cellulose triacetate membranes, Radiation Physics and
maintained at over 80% after 14 days stopped irrigation chemistry, Vol. 64, pp.149-160
[6] FengJun Hua (2001), Synthesis of self-crosslinking sodium
polyacrylate hydrogel and water-absorbing mechanism, Journal
of Meterial Science, Vol. 36, pp. 731-738
[7] Simano Margutti, Silvia Vicini, Noemi Proietti, Donatella
Capitani, Giuseppina Conio, Enrico Pedemonte, Anna Laura
Segre (2002), Physical-chemical characterisation of acrylic
polymers grafted on cellulose, Polymer, Vol 43, pp. 6183-6194
[8] Tran Thi Nhu Mai, Nguyen Thi Hong Hanh (2009), Synthesis of
swelling polymers from acrylic acid- survey the possibility of
exchange of water and micronutrients, Journal of Chemistry and
Application, No 7(91), pp. 41-44
[9] Hongliang Kang, Wenyong Liu, Benqiao He, Dawa Shen (2006),
Fig. 9. The amount of water content in the tree after 0 day, Synthesis of amphiphilic ethyl cellulose grafting poly(acrylic
7 days and 14 days stopped watering acid) copolymers and their self-assembly morphologies in water,
Polymer, Vol. 47, pp. 7927-7934
[10] Misnistry of Health – Institute of Nutrition (2007), The Food
IV. CONCLUSIONS ingredients in VietNam, Medical Publishing, Ha Noi
[11] Nguyen The Hung, Nguyen The Hung, Pham Xuan Thuong,
Nguyen Viet Long, Nguyen Van Loc, Nguyen Thi Hong Hanh
The swelling polymers was synthesize from cellulose by (2013), Use of germinating organic bag and substrate to grow
the graft reaction acrylic acid on to the cellulose chains. vegetables in Gia Lam, Ha Noi, Journal of Science and
Some physical methods (IR, XRD, SEM, EDX…) were Development, Vol. 11(7), pp. 909-916
used to determine the structure of the products, that [12] Nguyen Thi Hong Hanh, Phung Thi Thu Ha (2017), Effect of
moisturizing polymers on growth, development and enhanced
indicated the graft reaction was occurred. The products has drought tolerance in mustard green (Brassica juncea), Vietnam
hight swelling, about 250 gram per gram polymer in Fournal of Agiricuture sciences, Vol 15, No.1, pp. 100-106.
distilled water and has well swell in acidic and basic
solution from pH = 3-11. Within the pH = 6-10 range, the AUTHOR’S PROFILE
sweling of polymers is stable, so that, the swelling
polymer can be used for all acid and alkaline soils. The Dr. Nguyen Thi Hong Hanh
results experimental on mustard green, this swelling Lecturer at Department of Chemistry, Faculty of
polymer can make the rate of seed germination increased Environmental, Vietnam National University of
Agriculture. Major: Organic chemistry,
11.94-16.56%, the plant heigh increase 18.63- 26.27%, the Environmental science.
leaf area increase 56.62- 62.53% compare with the control Email: [email protected]
treatment. This swelling polymer is capable of maintaining /[email protected]
moisture for tree under conditions lack of water.

Copyright © 2017 IJAIR, All right reserved

37