Hydrogels from Poly (Acrylic Acid)/Carboxymethyl Cellulose & Poly (Acrylic Acid)/Methyl Cellulose

Hydrogels from Poly (Acrylic Acid)/Carboxymethyl Cellulose & Poly (Acrylic Acid)/Methyl Cellulose
V. Rivas-Orta, R. Antonio-Cruz, A.M. Mendoza-Martnez, A.B. Morales Cepeda and M.J. Cruz-Gmez
Copyright AD-TECH; licensee AZoM.com Pty Ltd. This is an AZo Open Access Rewards System (AZo-OARS) article distributed under the terms of the AZoOARS http://www.azom.com/oars.asp which permits unrestricted use provided the original work is properly cited but is limited to non-commercial distribution and reproduction. AZojomo (ISSN 1833-122X) Volume 2 July 2006 DOI: 10.2240/azojomo0267

Topics Covered Abstract Keywords Introduction Experimental Procedure Materials Synthesis of PAA/CMC and PAA/MC Hydrogels Films Characterization Determination of Hydrogels Water Absorbency Results and Discussion FTIR Spectroscopy Differential Scanning Calorimetry (DSC) Study of Surface Morphology Swelling Studies Conclusions Acknowledgements References Contact Details Abstract Hydrogels are hydrophilic polymeric networks with sensitivity to swelling transitions which are dependent on pH, temperature and ionic forces of surrounding environment or any other solvents [1]. New blends based on carboxymethyl cellulose (CMC) and poly (acrylic acid) (PAA) with methyl cellulose (MC), were prepared as thin films to be applied as a controlled system for drug release. Swollen PAA/CMC and PAA/MC hydrogels were prepared in water at different temperatures (30, 40 and 50C) and different pH values (acid, neutral and basic). PAA/CMC hydrogels with a 1135% swelling were obtained at 30C and pH 2.0, while PAA/MC hydrogels at 1082% swelling were obtained at 30C and pH 13.0. Initial films were analyzed by Fourier transformed infrared spectroscopy (FTIR) and the presence of functional groups of each polymer was confirmed and no secondary reactions were detected. Differential scanning calorimetry (DSC) indicated two glass transition temperatures (Tg); at 106C corresponding to PAA and 150C and 125C, corresponding to CMC and MC, respectively. Surface morphology was analyzed by Scanning electron microscopy (SEM) showing a less rough surface with increasing cellulose content in hydrogels. Keywords CMC, MC, Poly (acrylic acid), Swelling, pH.

July 2008 | Volume 4

Page 1 of 9

DOI: 10.2240/azojomo0267

V. Rivas-Orta, R. Antonio-Cruz, A.M. Mendoza-Martnez, A.B. Morales Cepeda and M.J. Cruz-Gmez

Introduction Super absorbent polymers have become an important component of many products due to their use in biomedical and pharmacobiologic fields such as personal hygiene items. Hydrogels are an example of such polymers since they are crosslinked materials capable of trapping a very large amount of water without being dissolved. Quantity of several used compounds as well as synthesis of mechanism have been rising quickly and that has allowed to obtain hydrogels with higher water swelling absorption than others and be able to have materials with highest swelling properties more than 99% in weight. The polymer mechanism is one of those responsible to swell a lot of aqueous solution volume but this mechanism is not only physics because not only depends of it besides the other responsible is polymer chemical nature. [2] Lately, hydrogels are used for controlled drug delivery systems when they are in contact with any surface. This could happen through channels or spaces inside the network and the matrix dissolution / disintegration (breaking up) effect. This process is possible due to the hydrogels response capacity to temperature changes, pH variation, ionic interactions, chemical compounds, etc. These materials showed a principal reaction by changing shape and volume. Hydrogels are interesting materials which have a lot of applications. The monomers used in this work were acrylic acid and cellulose derivates. Poly (acrylic acid) is a polyelectrolyte polymer able to form ions when subjected to an aqueous environment causing considerable volume swelling due to Hydrogen Bridge or covalent bond formation. This property is an important advantage for hydrogels made from poly (acrylic acid) and must be considered. PAA is not toxic and is very sensitive to temperature and pH changes. Recent studies about swollen hydrogels based on poly (acrylic acid) showed good mechanical and physical characteristics such as elongation, strain, tension resistance, among other properties. On the other hand, cellulose derivates have high rigidity; some can swell and be soluble in water or solvents depending on the extent of their degree of substitution. They can provide biodegradable character to any material when they are mixed with other materials since they are polysaccharide derivates. They can also enhance physical hydrogel properties. Therefore, a study of chemically crosslinked acrylic acid with several cellulose derivates such as: carboxymethylcellulose (CMC) and methyl cellulose (MC) was carried out in order to see the impact of each cellulose derivative on hydrogel properties and determine a probable application of the material as controlled drug release system. Thus PAA/CMC and PAA/MC hydrogels were prepared by chemical crosslinking with glutaraldehyde (GA) and N,N-methylene bisacrylamide (NN-MBA) using potassium persulphate (KPS) as initiator and hydrochloric acid (HCl) as catalyst, in aqueous solution. All samples were characterized by FTIR spectroscopy, DSC and SEM. Moreover, their swelling behavior at different temperatures and different pH values were measured. Experimental Procedure Materials CMC (Mw 90,000 degree of substitution 0.7), MC (Mw 14,000, degree of substitution (methoxy) 1.6-1.9) were supplied by Aldrich Chem. Co. Glutaric dialdehyde, 25 wt.% solution in water (glutaraldehyde) for synthesis was purchased from Merck-Schuchardt. Hydrochloric acid, 37 wt.% in water, was supplied by Fermont. Potassium persulfate (K2S2O8) was supplied by Fisher-Chemical Products Monterrey, S.A. N, N-Methylenbisacrylamide, 99% (MBA) crosslinking agent was purchased from Aldrich Chem. Co. Acrylic acid, 99% was supplied by Aldrich Chem. Co., and the water was double distilled. Synthesis of PAA/CMC and PAA/MC Hydrogels Films As suitable examples of hydrogels, we have chosen the hydrogels of PAA/CMC and PAA/MC with composition ratios of 75/25, 50/50, 25/75. Hydrogels composed of PAA and cellulose derivates (DC) were prepared by free radical solution polymerization in the presence of a crosslinker agent. For the cellulose derivates GA (2.5 X 10-3 M) and HCl (1.0 x 10-2) were used as
July 2008 | Volume 4 Page 2 of 9 DOI: 10.2240/azojomo0267

Hydrogels from Poly (Acrylic Acid)/Carboxymethyl Cellulose & Poly (Acrylic Acid)/Methyl Cellulose

crosslinker and catalysts respectively. The AA was crosslinked by using N,N-MBA and KPS as reaction initiator. Percentage of KPS and MBA were changed and tested between three values: 1%, 3% and 5% for KPS and 1% and 3% for MBA. The crosslinked hydrogels were prepared using various composition ratios in aqueous solution for CMC and MC (5 wt% solution). These CMC and MC solutions are partially homogeneous. The polymerization process was carried out under inert atmosphere (N2) to avoid oxidation. The solutions were heated to 80C with constant stirring for 30 minutes. GA (1 wt%) and MBA (1 wt%) were used as cross-linker for each hydrogels. KPS as initiator (0.5 wt% of total AA monomer) and HCl as catalyst were also added to the mixture and placed at 80C temperature in polyethyleneglycol bath for 3 h following the procedure given elsewhere [2-4] with minor changes. The mixture was then poured into a small Petri dish to obtain a film by slow drying at 60C for one week. Films were stored in an open dish overnight at 50C to allow solvent evaporation which led to their flexibility. Xerogels films were washed with water several times in order to eliminate the water soluble impurities and un-reacted monomer. Characterization The samples were characterized by Fourier Transform Infrared Spectroscopy (FTIR) was done on a Perkin Elmer Instruments Spectrum One model, using the KBr disc technique. Differential scanning calorimetry (DSC) was done on a TA Instruments 2010 model under nitrogen atmosphere, by heating from 0 to 200C at 10C/min rate in the first thermal cycle, and at 5C/min rate in a second thermal cycle. A sample weight of 10 2 mg was used in each case. The surface morphologies of hydrogels were examined using a scanning electron microscope JEOL JSM 5900 with an operating voltage of 5 Kv. Determination of Hydrogels Water Absorbency Hydrogels swelling was done at three different temperatures; 30, 40 and 50C, and at three different pH values (2, 7 and 13). Completely dried hydrogels samples were cut into pieces and weighed until obtained 0.4 g. Afterwards, each sample was placed in a glass vial with a lid; the sample was left to swell in a solution at the desired pH (2, 7 and 13) and constant temperature (30, 40 and 50C). The water absorbed in the hydrogels films after swelling was calculated from the relation: % Swelling (WC) = [(WS WD) / WD)] x 100 (1) Where WC is the hold water in percentage absorbed by the hydrogel film after 288 hours swelling, and WS and WD are hydrogel film weights after and before swelling, respectively. Results and Discussion The solid films of PAA/CMC were little opaque and PAA/MC films were transparent and clear. The crosslinking took place through the reaction between the hydroxyl group of the DC and the aldehyde groups of GA. FTIR Spectroscopy The infrared spectra of samples of PAA/CMC and PAA/MC, in the form of films, are shown in the Figure 1. The spectrum of the films shows the characteristic stretching absorptions of PAA/CMC and PAA/MC at 75/25 ratio. Figure 1 (A) at 3200 cm-1 shows a wide pronounced corresponding to OH bending from COOH group that posses PAA according to Dimitrov et al. [5] At 3594 cm-1 a weak band appears due to OH group free. The presence symmetric stretching of the carbonyl group (C=O) is shown at 1706 cm-1 and the C-O-H bending corresponding to pendant group (COOH) of PAA is shown at 1412 cm-1. Thus, the presence of PAA in films was confirmed. At 3325 cm-1 shows a weak band due to OH stretching which is present in CMC structure. CH stretching at 2881 cm-1 belongs to MC as shown in Figure 1 (B). The IR spectrum of PAA/MC (Figure1 (B)) contains a medium intensity band at 3478 cm-1 corresponding to OH stretching attributed to 2, 3 and 6 carbons from AGU structure for MC. Also, one weak to medium band is located at 2933 cm-1 and 2837 cm-1, which correspond to CH3 asymmetric and symmetric stretching, respectively. At 1034 cm-1 appears an intense band corresponding to C-O due to stretching of cellulose main structure.

July 2008 | Volume 4

Page 3 of 9

DOI: 10.2240/azojomo0267

V. Rivas-Orta, R. Antonio-Cruz, A.M. Mendoza-Martnez, A.B. Morales Cepeda and M.J. Cruz-Gmez

1706

1034

Absorbance, A /%

1412

3478

2933 2837

(
3594 1706 3200 1412 1034

(
3730 3230 2730 2230 1730 1230 730 wavenumber, wn / cm-1

Figure 1. FTIR Spectra of (A) 75PAA/25CMC hydrogel, (B) 75PAA/ 25MC hydrogel using 1% KPS and 1% MBA. Differential Scanning Calorimetry (DSC) The phase state was inferred from the number, location and shape of the glass transition evaluated by means of differential scanning calorimetry. The employed condition states that two polymers are immiscible if two separate glass transition temperatures which are characteristic for each polymer are detected, while they are miscible. If only one single Tg, an intermediate temperature is observed. The transition temperatures are listed in Table 1. Physical blends showed two transition temperatures (Tg) indicating that there are two separate phases, therefore, two to three-dimensional networks are in the hydrogel, one for PAA network and the other for cellulose derivates network. Based on this, it can be assumed that a semiinterpenetrating network was formed. Only one network was formed by polymerization and reticulation of AA while the other network was formed by crosslinking GA with cellulose derivates (CMC and MC). Crosslinking causes a Tg increment value to a higher temperature according to the Tg for each monomer. Results are shown in Table 1. These results indicate that when MBA amount increases, Tg value increases because the density of crosslinking is enhanced and therefore the sample needs more heat flow to make the first molecular structure movement. In other words, there is not enough volume necessary to make free movements between pendant groups or crosslinked networks due to reduced molecular space present in the hydrogel. Table 1. PAA/CMC and PAA/MC hydrogels Glass Transition temperatures with different amount of crosslinking agent (MBA) at 1% KPS.

July 2008 | Volume 4

Page 4 of 9

DOI: 10.2240/azojomo0267

Hydrogels from Poly (Acrylic Acid)/Carboxymethyl Cellulose & Poly (Acrylic Acid)/Methyl Cellulose

Composition ratio PAA/CMC 1% KPS 75/25-1% MBA 75/25-3% MBA 75/25-5% MBA Composition ratio PAA/MC 1% KPS 75/25-1% MBA 75/25-3% MBA 75/25-5% MBA 126 120 131 140 141 145 Tg PAA (C) Tg MC (C) 109 114 128 155 155 154 Tg PAA (C) Tg CMC (C)

Study of Surface Morphology The hydrogel surface morphologies for PAA/CMC and PAA/MC films prepared with 1% KPS and 1% MBA are shown in Figure 2. Figure 2 (A, B and C) shows more uniform surface when quantity of CMC was increased in the sample. Figure 2 (D and E) shows the rough outside surface due to high content of PAA, which makes an irregular surface. Also, it can be seen that when MC is introduced in the PAA/MC polymer blend, contributes to produce a less rough surface. The presence of spherical forms on the surface of the films shown in Figure 2 (E) indicated that two types of PAA exist, one in crosslinked way and the other as linear polymer. When PAA is present in the non-crosslinked form, it causes entanglements which are represented by these small spherical forms. However, the surfaces of the films are soft to the touch.

A)

July 2008 | Volume 4

Page 5 of 9

DOI: 10.2240/azojomo0267

V. Rivas-Orta, R. Antonio-Cruz, A.M. Mendoza-Martnez, A.B. Morales Cepeda and M.J. Cruz-Gmez

B)

C)

D)

E) Figure 2. SEM pictures of PAA/CMC & MC films with 1% MBA and 1% KPS : A) 100PAA, B)

July 2008 | Volume 4

Page 6 of 9

DOI: 10.2240/azojomo0267

Hydrogels from Poly (Acrylic Acid)/Carboxymethyl Cellulose & Poly (Acrylic Acid)/Methyl Cellulose

75PAA/25CMC and C) 25PAA/75CMC and for PAA/MC: D) 100PAA/0MC, E) 50PAA/50MC. Swelling Studies Figure 3 showed the effect of pH on the %swelling of the PAA/CMC hydrogels tested at 30C and different pH values with 1% KPS and 3% MBA. In this test, the quantity of water absorbed by the PAA/CMC films with 25/75 composition ratio was found to be the highest with respect to the other compositions, indicating that CMC predominates in the matrix exhibiting superabsorbent characteristics. Figure 3 showed the films respond much better when were placed in acid solutions due to the presence of Na cations in CMC, which allowed ionic bonds with anions present in acid solutions. It is worth mentioning that the hydrogels which have maximum absorption have 3% MBA. If crosslinking density is higher and the free spaces inside the three-dimensional hydrogel are lower, the Cl ions (Cl-) are bigger than these spaces. Therefore, the cations (Na+) have more possibilities to incorporate with the ionized structure of the hydrogel. Figure 4 showed the maximum swelling percentage of PAA/MC films was 1082% with 75/25 composition ratio, tested at 30C and pH=13. Because the MC pendant group ( CH3) is smaller than CMC pendant group (-CH2COONa), when the network were placed in basic solutions, the NH3 ions have less hysteric impediment because they have more spaces been able to form Van der Waals bridge with free existent OH. This behavior was reflected with volume increase due to water absorption. Furthermore, the final structure contain 3% MBA, therefore, there are additional oxygen (=O) content in network that increase the probability to enhance absorption, that is to say, free available spaces is founded to form Van der Waals bridge. The most important characteristic was the hydrogels held the water for a long period of time without morphology change.

1200 1000 Swelling, S / % 800 600 400 200 0 75/25 50/50 Composition ratios, PAA/CMC / % 25/75

13

Figure 3. Effect of pH on the % swelling of the PAA/CMC hydrogels tested at 30C with 1% KPS and 3% MBA.

July 2008 | Volume 4

Page 7 of 9

DOI: 10.2240/azojomo0267

V. Rivas-Orta, R. Antonio-Cruz, A.M. Mendoza-Martnez, A.B. Morales Cepeda and M.J. Cruz-Gmez

1200

1000

Swelling, S / %

800

600

400

200

0 75/25 50/50 Composition ratios, PAA/MC / % 25/75

13

Figure 4. Effect of pH on the % swelling of the PAA/MC hydrogels tested at 30C with 1% KPS and 3% MBA. Conclusions PAA and CMC and MC were crosslinked to different concentrations of MBA and KPS in order to observe changes in their properties. The characterization by means FTIR indicates the presence of the poly (acrylic acid) crosslinking with cellulose derivates. DSC analysis showed two glass transition temperatures in all samples for two types of hydrogels (PAA/CMC and PAA/MC). Therefore it is concluded that the films are formed by two homogeneous three-dimensional networks. SEM pictures indicated the presence of PAA and cellulose derivates. PAA/CMC and PAA/MC hydrogels showed that the best temperature for water absorption was 30C in both hydrogels. The difference in water absorption between PAA/CMC and PAA/MC is due to pH. CMC showed more compatibility with acid ions (Cl-) in acid solution due to Na+ cations which are present in this derivate. On the other hand, the MC showed compatibility with NH4+ cations due to the electronegative site in this derivative. Acknowledgements The authors are grateful to Secretaria de Educacin Pblica (SEP) and Direccin General de Educacin Superior Tecnolgica (DGEST) for generous financial support with key UR612. One of us (V. R. O.) wishes to thank the Consejo Nacional de Ciencia y Tecnologa (CONACYT) for a fellowship with number 181664. References
1. 2. 3. 4. 5. Soo Shin H., S. Yeon Kim and Y. Moo Lee., Permeation of Solutes Through Interpenetrating Polymer Network Hydrogels Composed of PVA and PAA, J. Applied P. Sci., (2004), 479-486. Escobar J.L., Garca D.M., Zaldivar D. and Katime I., Influencia de la Temperatura en el Proceso de Hinchamiento en Hidrogeles de Poli(N-isopropilacrilamida - co-N,N-Dimetilacetamida), Revista Iberoamericana de Polmeros, 3(1) (2001). Park JS., Park JW. and Ruckenstein E, Thermal and Dynamic Mechanical Analysis of PVA/MC Blend Hydrogels, J. Appl Polym Sci., 42 (2000). Thiel J. and Maurer G., Swelling Equilibrium of Poly(acrylamide) Gels in Aqueous Salt and Polymer Solutions, Fluid Phase Equilibria, 165 (2000) 225-260. Dimitrov M., Lambov N., Shenkov S., Dosseva V. and Baranovski V., Hydrogels Based on the Chemically Crosslinked Polyacrylic Acid: Biopharmaceutical Characterization, Acta Pharm., 53 (2003) 25-31.

Contact Details V. Rivas-Orta, R. Antonio-Cruz, A.M. Mendoza-Martnez and A.B. Morales M.J. Cruz-Gmez Universidad Nacional Autnoma de Mxico

July 2008 | Volume 4

Page 8 of 9

DOI: 10.2240/azojomo0267

Hydrogels from Poly (Acrylic Acid)/Carboxymethyl Cellulose & Poly (Acrylic Acid)/Methyl Cellulose

Cepeda Instituto Tecnolgico de Ciudad Madero (ITCM) Divisin de Estudios de Posgrado e Investigacin Juventino Rosas y Jess Urueta S/N, Col. Los Mangos, C.P.89440, Cd. Madero, Tamp. Mxico E-mail: orta_valeria@yahoo.com E-mail: rantonio70@yahoo.com

(UNAM) Facultad de Qumica Departamento de Ingeniera Qumica Cd. Universitaria, Mxico, D.F. 04510 Mxico

This paper was also published in Advances in Technology of Materials and Materials Processing Journal, 9[2] (2007) 167-172.

July 2008 | Volume 4

Page 9 of 9

DOI: 10.2240/azojomo0267