PREPARING CELLULOSE/POLY(VINYL

ALCOHOL)/CURCUMIN BLENDS USING AN IONIC LIQUID

P. F. M. Pereira1, C. T. Andrade2

1- Programa de Ps-Graduao em Cincia de Alimentos Universidade Federal do Rio de Janeiro, Instituto de

Qumica CEP: 21941-909 Rio de Janeiro RJ Brasil e-mail: (pamelafreire@ufrj.br)
2- Programa de Ps-Graduao em Cincia de Alimentos Universidade Federal do Rio de Janeiro, Instituto de
Macromolculas CEP: 21941-598 Rio de Janeiro RJ Brasil e-mail: (ctandrade@ima.ufrj.br)

ABSTRACT Biopolymer blends from ionic liquids consist of an alternative to the preparation of
materials with improved characteristics. Accordingly, cellulose/poly(vinyl alcohol)/curcumin films
were prepared by dissolution/regeneration from the ionic liquid 1-allyl-3-methylimidazolium chloride
(AMIMCl). SEM micrographs and XRD data revealed the compatibilizing effect of IL. Fourier
transform infrared spectroscopy (FTIR) weas used to investigate molecular interactions in the blends.
The films showed an intermediate water solubility comparing with the control.

KEYWORDS: cellulose; poly(vinyl alcohol); ionic liquid; biopolymeric blends.

1. INTRODUCTION

Biopolymers and their blends have been studied as alternatives for preparation of
biodegradable materials in order to reduce the environment impact, triggered by synthetic plastic waste.
Among biopolymers, cellulose is the most abundant natural polymer, has many attractive properties
such as low cost, renewability, biodegradability, non-toxicity, and biocompatibility However, its
processability is difficult, due to the complexity of the biopolymeric network, partially crystalline
structure and extended non-covalent interactions among molecules, which exert a strong influence on
the solubility of the polysaccharide (Medronho and Lindman, 2015). On the other hand, ionic liquids
(IL) have been extensively studied as cellulose solvents, mainly because of their attractive properties
such as good chemical and thermal stability, low melting point, low flammability and negligible vapor
pressure. Moreover, new materials may be obtained because IL can act as plasticizer, coupling and
compatibilizing agents (Shamsuri and Daik, 2015).
Cellulose can play a substantial role when blended with other polymers to produce new
materials. When cellulose is blended with a synthetic polymer, the ratio cost-performance is increased;
synthetic polymers have low production costs and the elaboration of those blends entail new materials
with improved physical and mechanical properties (Kanatt et al., 2012). In this context, some authors
reported the successful preparation of cellulose/PVA materials from regeneration of different ionic
liquids (Hameed et al., 2013).
The incorporation of natural substances to synthetic or natural polymers, with the aim of
introducing some properties, such as antioxidant (Iahnke et al., 2016), antimicrobial (Luo et al., 2012),
and pH indicators (Gutirrez et al., 2016) have attracted the attention of researches. In the special case
of biopolymers, the incorporation of natural biomolecules is interesting, because preserves the
biodegradable characteristics of materials.
 In this study, with the aim of producing intelligent films for food packaging,
cellulose/poly(vinyl alcohol) blended films, incorporated with curcumin, were obtained from the
regeneration of an ionic liquid. The compatibilization of the polymer pair was evaluated. The role of
each polymer on some properties of the films was investigated.

2. MATERIALS AND METHODS

2.1. Materials
Microcrystalline cellulose in powder, 1-methylimidazol (99%), allyl chloride and poly(vinyl
alcohol) were obtained from Sigma Aldrich (So Paulo, SP, Brazil). Curcumin dye powder BCP-900
(97.26% of curcumin) was donated by Baculer (Olmpia, SP, Brazil). All materials were used without
any previous purification.

2.2. Preparation of cellulose/PVA/curcumin films

The ionic 1-allyl-3-methylimidazolium chloride (AMIMCl) was synthesized according to the
method proposed by Zhang et al. (2005). 1-Methylimidazolium and allyl chloride were mixed at a 1:1.25
molar ratio at 55C for 8 h. The amber viscous liquid was purified in a rotavapor to remove excess of
reagents and other impurities. To verify the effect of each biopolymer on the blend properties, a central
composite design 2 (Table 1) was used. The biopolymers were pre-mixed in the presence AMIMCl at
room temperature for 10 min. Then, the mixture was heated under magnetic stirring at 85C for 2 h.
Approximately 3 g of each filmogenic solution were cast on polyethylene dishes and regenerated
immediately with distilled water. To verify the removal of the ionic liquid from the films, the AgNO3
test was used until no Cl- ions were detected. Finally, the films were dried at 50C for 6 h and removed
from the plates to be characterized.

2.3. Characterization
The morphology of the films was evaluated at their cryo-fractured surfaces, using a scanning
electron microscope (SEM) TM3030plus (Hitachi, Chiyoda, Japan) operated at 15 kV. The samples
were coated by a thin gold layer using a sputter coating SCD 005 (Baltec, Balzers, Liechtenstein).
The films were analyzed by a Miniflex X-ray diffractometer (Rigaku Corporation, Tokyo,
Japan) equipped with Cu-K radiation source ( = 1.542 ) operating at 30 kV and 15 mA. The
diffractograms were recorded in the 2 angular region of 2 - 40 at a rate of 0.05/s.
FTIR spectra of the films were obtained with a Varian Excalibur 3100 spectrometer
(Mulgrave, Australia). The transmittance spectra were collected with a 4 cm-1 resolution between 4000
a 600 cm-1, using the attenuated total reflectance (ATR) technique.
The water solubility of the films was evaluated by drying the samples (20 mm x 20 mm) at
100C for 24 h. The films were put in a desiccator and weighed to determine the initial mass (Mi). Then,
the films were immersed in 50 mL of distilled water for 24 h, dried at 100C for 24 h and weighed to
determine the final mass (Mf). The water solubility was determined as the percent difference between
the initial and final masses.
3. RESULTS AND DISCUSSION

Scanning electron microscopy (SEM) was used to evaluate the morphology of the films and
the possible compatibilization between the cellulose/PVA/curcumin films components. The
micrographs of transversal sections, obtained through cryogenic fractures of the films are shown in
Figure 1. The films showed good adhesion between the phases and no evidence of incompatibility
between the polymeric materials was founded. This result suggests that the ionic liquid AMIMCl acted
successfully as a common solvent and a compatibilizing agent for these materials.

Figure 1. Micrographs of transversal section obtained from Cel/PVA/Curcumin films at different

proportions of polymers: (a) 4:0; (b) 3:3; (c) 3:5; (d) 5:3; (e) 5:5; (f) 2.59:4; (g) 5.41:4; (h) 4:2.59; (i)
4:5.41; (j) 4:4.

a b c d e

f g h i j

Some authors reported the elaboration of new biopolymer materials from blends of immiscible
polymers, compatilibized through addition of ionic liquids, such as Cellulose/PVA using BMIMCl
(Hameed et al., 2013). Thus, the ionic liquid, in addition of acting as a common solvent for the polymers
used for elaborating blends and composite materials, could act as a compatibilizing agent.
The X-ray diffraction technique is commonly applied to evaluate the degree of crystallinity of
different materials. Native cellulose (Fig. 2a, trace I) showed characteristic reflections around 2=
14.9, 16.7, 22.5 e 34.5, similarly to results reported in the literature (Wu et al., 2012). However, in
the diffractogram obtained for regenerated cellulose (Fig. 2b, trace I), the reflections were shifted to
2= 14.8, 17.1and 20.85 and had their intensities severely reduced. This result indicate that the
process of dissolution/regeneration caused changes in crystalline structure of cellulose.
The Cel/PVA/Curcumin films (Fig. 2b e 2c) showed reflections in the region 2= 20-23.
With the increase in the PVA concentration, the reflections were less intense and were maintained in the
same region. Generally, in the case of polymeric blends, the decrease in reflections intensity is attributed
to increasing compatibility. Therefore, the observed results from X-ray data corroborated the SEM
results.
Figure 2. Diffractograms for (a) microcrystalline cellulose (I); PVA (II) and curcumin (III); (b)
regenerated cellulose (I) andCcel/PVA/curcumin films at different proportions of Cel:PVA; 3:3 (II), 3:5
(III), 5:3 (IV) and 5:5 (V); (c) 2.59:4 (I), 5.41:4 (II), 4:2.59 (III), 4:5.41 (IV) and 4:4: (V).
(a) (b) (c)
I I

I II II
II
III III

IV IV

III V V

0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
2() 2() 2()

Fig. 3 shows the FTIR spectra obtained for the microcrystalline cellulose, PVA and curcumin
(Fig. 3a) and their films (Fig. 3b,c). All Cel/PVA/Cur films showed an absorption at 1020 cm-1, which
is associated to stretching of CO groups present in cellulose, PVA and in curcumin. Comparing Fig.
3b and 3c, it can be observed that the FTIR spectra of the films showed a dependence on the polymer
composition. Moreover, a clear profile change in the hydroxyl stretching region was detected, which
showed wider and more intense peaks for films IV (Fig. 3b), I (Fig. 3c) and IV (Fig. 3c). This result
might indicate that, for these films, the good adhesion among the phases (Fig. 1), could be related to
hydrogen bonds formed among the components molecules. On the other hand, films II (Fig. 3b) and II
(Fig. 3c), showed a tendency of the OH stretching region disappearance. For these films, the SEM
images (Fig. 1) showed a rough surface.

Figure 3. FTIR spectra of (a) Microcrystalline cel (I); PVA (II) and curcumin (III); (b) regenerated cel
(I) and for Cel/PVA/Curcumin films at different proportions of Cel:PVA : 3:3 (II), 3:5 (III), 5:3 (IV)
and 5:5 (V); (c) 2,59:4 (I), 5,41:4 (II), 4:2,59 (III), 4:5,41 (IV) and 4:4: (V).
(a) (b) I (c) I
I
II
Transmitance (A. u)
Transmitance (A. u)

Transmitance (A. u)

III
II
IV II

III

IV
III
V V

4000 3500 3000 2500 2000 1500 1000 4000 3500 3000 2500 2000 1500 1000 4000 3500 3000 2500 2000 1500 1000

Wavenumber (cm-1) Wavenumber (cm-1) Wavenumber (cm-1)

The water solubility (WS) of the films is shown in Table 1. Comparing the results of WS for
the blends with that found for regenerated cellulose, it can be seen that there was a notable increase in
this property for blends. The intermediate solubility of the Cel/PVA/Curcumin blends could be
attributed also to the anisotropic character of cellulose (Medronho and Lindman, 2015) in combination
with PVA affinity for water.
 Table 1. Central composite design matrix used to study Cel/PVA/Curcumin films at a curcumin
fixed concentration (1 g/100 mL).
Cellulose concentration PVA concentrarion Water solubility
Treatments
(g/100 mL) (g/100 ml) (%)
1 3.00 3.00 21.13,5
2 3.00 5.00 40.01,7
3 5.00 3.00 30.51,8
4 5.00 5.00 40.65,7
5 2.59 4.00 36.23,3
6 5.41 4.00 30.41,5
7 4.00 2.59 23.30,7
8 4.00 5.41 52.91,1
9 4.00 4.00 28.73,0
10 4.00 4.00 30.24,4
11 4.00 4.00 29.50,8
Control 4.00 - 5.31,2

Figure 4. Water solubility (WS) response for the different films studied as a function of cellulose
concentration (CC) and PVA concentration (PVA).

According to Fig. 4, it is possible to verify that the higher content of PVA in the films results
in a higher water solubility. This result was expected, because of the high affinity of PVA for water.
However, the addition of PVA at concentrations lower than those correspondent to the central points,
and in combination with any concentration of cellulose, resulted in films with a lower solubility.

4. CONCLUSION

Cel/PVA/Curcumin films were successfully obtained. SEM micrographs and XRD data
revealed the role of the ionic liquid as a compatibilizing agent for the immiscible polymeric pair. FTIR
spectra suggested that the films components interacted by hydrogen bonds. The films showed
intermediate water solubilities, due to the hydrophilic character of both biopolymers, mainly affected
by the PVA content and its interaction with Cel and curcumin.

5. ACKNOWLEGMENT

The authors thank CNPq, CAPES and FAPERJ for financial support and Baculer company for
donating the curcumin dye.

6. REFERENCES

Gutirrez, T. J., Suniaga, J., Monsalve, A., Garca, N. L. (2016) Influence of beet flour on the
relationship surface-properties of edible and intelligent films made from native and modified plantain
flour. Food Hydrocolloids, 54 (1), 234-244.

Hameed (2013). Fabrication and characterization of transparent and biodegradable cellulose/poly(vinyl

alcohol) blend films using an ionic liquid, Cellulose, 20(1), 2517-2577.

Iahnke, A. O. S., Costa, T. M. H., Rios, A. O., Flres, S. H. (2016). Antioxidant films based on gelatin
capsules and minimally processed beet root (Beta vulgaris L. var. Conditiva) residues. J. Appl. Polym.
Sci., 133 (10).

Kanatt, S. R., Rao, M. S., Chawla, R. S. P., Sharma, A. (2012). Active chitosan-polyvinyl alcohol films
with natural extracts. Food Hydrocolloids, 29(1), 290-297.

Luo, N., Varaprasad, K., Reddy, G. V. S., Rajulu, A. V., Zhang, J. (2012). Preparation and
characterization of cellulose/curcumin composite films, RSC Advances, 2, 8483-8488.

Medronho, B., Lindman. (2015).Brief overview on cellulose dissolution/regeneration interactions and

mechanisms, Advances in Colloid and Interface Science, 222(1), 502-508.

Shamsuri, A. A. & Daik, R. (2015) Applications of ionic liquids and their mixtures for preparation of
advanced polymer blends and composites: a short review. Rev. Adv. Mater. Sci., 40(1) 45-59.

Wu, Y., Fu, Z., Yin, D., Xu, Q., Liu, F., Lu, C., Mao, L. (2012) Microwave-assisted hydrolysis of
cristalline cellulose catalyzed by biomass char sulfonic acids. Green Chemistry, 12(1), 696-700.

Zhang, H., Wu, J., Zhang, J. He. J. 1-Allyl-3-methylimidazolium chloride room temperature ionic
liquid: A new and powerful nonderivatizing solvent for cellulose. Macromolecules, 38(1), 8272-8277.