Studies on Poly(acrylic acid)/Attapulgite Superabsorbent Composite. I.

Synthesis and Characterization

An Li, Aiqin Wang, Jianmin Chen
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
Received 2 July 2003; accepted 3 October 2003

ABSTRACT: A novel poly(acrylic acid)/attapulgite superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) on attapulgite micropowder using N,N-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator in aqueous solution. The effects on water absorbency of such factors as reaction temperature, initial monomer concentration, degree of neutralization of AA, amount of crosslinker, initiator, and attapulgite were investigated. These crosslinked superabsorbent composites were characterized by thermogravimetetric analysis and scanning electron microscopy. The graft copolymerization reaction of AA on attapulgite micropowder was characterized by FTIR. The water

absorbencies for these superabsorbent composites in water and saline solutions were investigated and water-retention tests were carried out. Results obtained from this study show that the water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% exhibited an absorption of 1017 g H2O/g sample and 77 g H2O/g sample in distilled water and in 0.9 wt % NaCl solution, respectively. 2004
Wiley Periodicals, Inc. J Appl Polym Sci 92: 1596 1603, 2004

Key words: acrylic acid; superabsorbent; crosslinking; water absorbency; water retention

INTRODUCTION Superabsorbents can absorb a large amount of water during a short period of time and the absorbed water can be removed only with difculty, even under some pressure. Therefore, superabsorbents have great advantages over traditional water-absorbing materials such as cotton, pulp, and sponge, and have found a variety of valuable applications.13 Because of their excellent characteristics, these superabsorbents are widely used in many elds such as agriculture and horticulture,4,5 sanitary goods,6 sealing composites,7 and medicine for drug-delivery systems,8 for example. The synthesis of new superabsorbents and the development of their applications are still interesting research areas. Recently, the preparation of organic inorganic superabsorbent composites has attracted great attention because of their relatively low production cost, high water absorbency, and their considerable range of applications in agriculture and horticulture. Zhu et al.9 reported the synthesis of poly(acrylic acid)/kaolinite superabsorbent composite by means of inverse suspension polymerization. Wu et al.10,11 prepared starch-g-polyacrylamide/clay and poly(acrylic acid)/mica superabsorbent composites by graft copolymerization reaction of organic monomer and inorCorrespondence to: A. Wang (waq03202002@sina.com). Journal of Applied Polymer Science, Vol. 92, 1596 1603 (2004) 2004 Wiley Periodicals, Inc.

ganic clay mineral powder. Attapulgite is a layered aluminum silicate with reactive OH groups on the surface. To reduce costs and improve the comprehensive water-absorbing properties of the superabsorbent materials, the grafting of acrylic acid polymer onto attapulgite and fabricating a composite that consists of polymer and attapulgite micropowder was considered a priority. In this article, we report the synthesis of superabsorbent composites by graft copolymerization reaction of acrylic acid on attapulgite micropowder using N,N-methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator in an aqueous solution. The effects on water absorbency of such factors as reaction temperature, initial monomer concentration, degree of neutralization of acrylic acid, amount of crosslinker, initiator, and attapulgite were investigated. EXPERIMENTAL Materials Acrylic acid (AA, chemically pure, Shanghai Wulian Chemical Factory, Shanghai, China) was distilled under reduced pressure before use. Ammonium persulfate (APS, analytical grade, Xian Chemical Reagent Factory, Xian, China) was recrystallized from water. N,N-Methylenebisacrylamide (MBA, chemically pure, Shanghai Chemical Reagent Corp., Shanghai, China) was used as purchased. Attapulgite micropowder (Xuyi Colloidal Co., Jiangsu, China) was milled

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through a 320-mesh screen, followed by a treatment with 37% hydrochloric acid for 48 h and washed with distilled water until pH 7 was reached, after which it was dried at 105C for 8 h before use. All solutions were prepared with distilled water.

Water-absorbency measurement A weighted quantity of the superabsorbent composite was immersed in distilled water at room temperature to reach the swelling equilibrium. Swollen samples were then separated from unabsorbed water by ltering over a 100-mesh screen. The water absorbency (QH2O) of the superabsorbent composite was determined by weighing the swelled samples, and the QH2O of the samples was calculated using the following equation: Q H2O m2 m1/m1 (1)

Preparation of superabsorbent composites A series of samples with different amounts of attapulgite, crosslinker, initiator, and acrylic acid with different degrees of neutralization were prepared by the following procedure. Typically, AA (7.2 g) was dissolved in 20 mL of distilled water and then neutralized at 5C with 12 mL of sodium hydroxide solution (5M) in a four-neck ask equipped with a stirrer, a condenser, a thermometer, and a nitrogen line. Attapulgite powder (0.8 g) was dispersed in the above partially neutralized monomer solution. Under nitrogen atmosphere, the crosslinker MBA (16.0 mg) was added to the AAattapulgite mixture solution and the mixed solution was stirred on a water bath at room temperature for 30 min. The water bath was then heated slowly to 70C with vigorous stirring after the radical initiator APS (80.2 mg) was charged to the mixed solution. After 3 h of the reaction, the resulting product was washed several times with distilled water and then dried in a vacuum oven at 60C to a constant weight. Thus, the superabsorbent composite was prepared after the dried product was milled and screened. All samples used had a particle size in the range of 40 80 mesh.

where m1 and m2 are the weights of the dry sample and the water-swollen sample, respectively. QH2O was calculated as grams of water per gram of sample. Characterization 1. The IR spectra of the superabsorbent composite were recorded on a Bio-Rad WIN FTIR (BioRad, Hercules, CA) using KBr pellets. The IR spectrum of the superabsorbent composite shows absorption bonds corresponding to the functional groups attached to the monomeric units. 2. Thermal stability studies of dry samples were performed on a PerkinElmer TGA-7 thermogravimetric analyzer (Perkin Elmer Cetus Instruments, Norwalk, CT), with a temperature range of 25 800C at a heating rate of 10C/min using a dry nitrogen purge at a ow rate of 50 mL/min. 3. The morphology of the dried polymer was examined using a JSM-5600LV SEM instrument after (JEOL, Ltd.) coating the sample with gold lm. RESULTS AND DISCUSSION

Preparation of uncrosslinked poly(acrylic acid) The preparation procedure of uncrosslinked poly(acrylic acid) [PAA] was similar to that of preparation of superabsorbent composite except without attapulgite and MBA.

Preparation of uncrosslinked PAA-grafted attapulgite AA (4.2 g) was dissolved in 15 mL of distilled water in a 250-mL four-neck ask equipped with a stirrer, a condenser, a thermometer, and a nitrogen line. Under nitrogen atmosphere, attapulgite micropowder (1.0 g) was added to the AA solution and the mixture was stirred at room temperature for 30 min. APS (40 mg) was added to the mixture, which was heated at 70C with stirring in a nitrogen atmosphere for 4 h. Then the reaction mixture was poured into a large volume of distilled water and the precipitate was ltered, dried in a vacuum oven at 40C, and weighed. Nongraft polymer was extracted from the precipitate with ethanol for 10 h.

Effect of initial monomer concentration The effect of initial AA concentration (CA, wt %) on water absorbency is shown in Figure 1. The water absorbency in distilled water decreased from 1288 to 361 g/g with the increase of CA from 14.0 to 31.5 wt %. It was difcult to obtain a composite gel in the preparation when CA was less than 14.0 wt % and water absorbency was hard to measure exactly because of the excessive water-soluble material. It was reported by Baker et al.12 that the effective crosslinking density is probably less than the nominal crosslinking density at a low total monomer concentration in the preparation of cationic acrylamide-based hydrogel. The result for PAA/attapulgite superabsorbent composite conformed to the resulting cationic acrylamide-based hy-

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Figure 1 Effect of initial AA concentration on water absorbency of superabsorbent composite in distilled water: reaction temperature, 70C; 60% neutralization degree; weight ratio of crosslinker, initiator, and attapulgite in the feed is 0.2, 1.0, and 10%, respectively.

Figure 3 Effect of crosslinker content on water absorbency of superabsorbent composite in distilled water: reaction temperature, 70C; 60% neutralization degree; CA, 17.2 wt %; weight ratio of initiator and attapulgite in the feed is 1.0 and 10%, respectively.

drogel and similar observations were reported by others.13,14 Effect of reaction temperature Figure 2 shows that the water absorbency of the superabsorbent composite increases as the reaction temperature increases from 40 to 70C and decreases with further increases in reaction temperature. When the

reaction temperature is decreased, the rate of polymerization also decreases, which results in the enhancement of crosslinking efciency.15 At the same crosslinker content, the water absorbency decreases with the increase of the crosslinking efciency according to Florys network theory.16 However, when the polymerization temperature is higher than 70C, the water absorbency is decreased. With the increase of reaction temperature, the polymerization reaction rate increases and the molecular weight decreases, so the water absorbency is also decreased. Effect of crosslinker content Crosslinking density is an extremely important swelling control element. Relatively small changes in crosslinking density can play a major role in modifying the properties of superabsorbent polymers. The effect of crosslinker content on water absorbency is shown in Figure 3. It can be seen that the water absorbency decreases with the increase of crosslinker content from 0.2 to 1.5 wt %. When the crosslinker content is 0.2 wt %, the absorbency of superabsorbent composite decreases because of an increase of soluble material. On the other hand, a higher crosslinker content results in the generation of more crosslink points, which in turn causes the formation of an additional network and decreases the space left for water to enter. The results are in conformity with Florys network theory16 and similar observations were previously reported by others.14,15

Figure 2 Effect of reaction temperature on water absorbency of superabsorbent composite in distilled water: 60% neutralization degree; CA, 17.2 wt %; weight ratio of crosslinker, initiator, and attapulgite in the feed is 0.2, 1.0, and 10%, respectively.

Effect of initiator content Figure 4 shows the effect of the initiator content on water absorbency. The water absorbency increases as

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Figure 4 Effect of initiator content on water absorbency of superabsorbent composite in distilled water: reaction temperature, 70C; 60% neutralization degree; CA, 17.2 wt %; weight ratio of crosslinker and attapulgite in the feed is 0.2 and 10%, respectively.

absorbency increases from 40 to 60% and decreases with further increases in the neutralization degree of AA. This behavior may be interpreted as a cooperative absorbing effect between carboxylic acid and carboxylate group that is superior to either group. According to Florys network theory, the swelling ability of ionic network is attributed to the rubbery elasticity, ionic osmotic, and afnity of polymer toward water. When poly(acrylic acid) is neutralized with sodium hydroxide, the negatively charged carboxyl groups attached to the polymer chains set up an electrostatic repulsion that tends to expand the network. In a certain range of neutralization degree, the electrostatic repulsion increases with the increase of neutralization degree, resulting in the increase of water absorbency. However, further increases in the neutralization degree of PAA result in the generation of more sodium ions, which reduce the electrostatic repulsion by screening the negative charges of carboxyl groups, thus resulting in the decrease of water absorbency. Under our experimental conditions, a neutralization degree of 60% of PAA possesses the highest water absorbency. Similar results were reported in previous studies.15,19 Effect of attapulgite The effect of the amount of attapulgite in the superabsorbent composite on the water absorbency is shown in Table I. When a prepared superabsorbent composite contained a small amount of attapulgite (5%), the water absorbency of the resulting product signicantly improved. When the content of attapulgite in superabsorbent composite was 5%, the water

APS content increases from 0.1 to 1.0 wt % and decreases with further increases in the content of APS. The relation between the average kinetic chain length (v) and concentration of the initiator in free-radical polymerization is given by the following equation17: v 1 2 K p fK i k t 1/2 I 1/2 M (2)

where kp, ki, and kt are the rate constants for propagation, initiator, and termination, respectively; f is the efciency of initiation by the initiator; and [I] and [M] are the initial concentration of the initiator and monomer, respectively. According to eq. (2), the molecular weight in free-radical polymerization will decrease with an increase of initiator concentration. With the decrease of the molecular weight, the relative amount of polymer chain ends increases. As reported in a previous study,18 the polymer chain ends do not contribute to the water absorbency. Therefore, the increase of initiator content is responsible for the decrease in water absorbency. However, further decreases in APS content below the optimum values are accompanied by a decrease in absorbency. This result may be attributed to a decrease in the number of radicals produced as the content of APS decreases. The network cannot form efciently with a small number of radicals in the free-radical polymerization that results in the decrease of the water absorbency. Effect of neutralization degree The effect of neutralization degree on the water absorbency is shown in Figure 5. It is obvious that the water

Figure 5 Effect of neutralization degree on water absorbency of superabsorbent composite in distilled water: reaction temperature, 70C; CA, 17.2 wt %; weight ratio of crosslinker, initiator, and attapulgite in the feed is 0.2, 1.0, and 10%, respectively.

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TABLE I Effect of Amount of Attapulgite on Water Absorbency of the Superabsorbent Compositesa

Attapulgite percentage (wt %) 0 5 10 20 35 QH2O (g/g) Distilled water 712 1325 1017 787 773 0.9 wt % NaCl 69 117 77 74 71

Sample PAA PA1 PA2 PA3 PA4

a

Reaction conditions: reaction temperature, 70C; 60% neutralization degree; CA, 17.2 wt %; weight ratio of crosslinker and initiator in the feed is 0.2% and 1.0%, respectively.

absorbency decreased with the increase of the amount of attapulgite. This may be attributed to the fact that a greater amount of attapulgite results in the generation of more crosslink points, which increases the crosslinking density of the superabsorbent composite and reduces the absorbency of the composite. The mechanism of polyacrylonitrile grafting onto mica was reported in a previous study.20 It was presumed that the hydroxyl groups in attapulgite may react with APS by a similar mechanism and liberate free radicals on the attapulgite structure and that the graft polymerization will take place on these free radicals, giving PAA branches on the attapulgite backbone as given in the following set of equations:

Si O O O Al O OH initiator 3 Si O O O Al O O Si O O O Al O O H 2C A CHCOOH 3 Si O O O Al O O P CH 2 P CHCOOH P CH 2 P CHCOOH

Infrared spectra The infrared spectrum of uncrosslinked PAA-grafted attapulgite is shown in Figure 6(a). This can be compared to the spectra of attapulgite and uncrosslinked PAA shown in Figure 6(b) and (c), respectively. The characteristic peak at 1717 cm1 arises from the carbonyl group CAO of PAA, which provides evidence of a graft polymerization reaction between PAA and attapulgite.

Thermal stability Thermogravimetic analysis (TGA) curves of crosslinked PAA and PA3 are shown in Figure 7(a) and (b), respectively. Both crosslinked PAA and PA3 show a very small weight loss below 100C, implying a loss of moisture. At around 240C, crosslinked PAA and PA3 have similar signicant weight losses of 10.0% (244C) and 9.3% (237C), respectively. The major weight loss

Figure 6 Infrared spectra of (a) poly(acrylic acid) grafted attapulgite, (b) attapulgite, and (c) uncrosslinked PAA.

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different temperatures (60 or 100C). It can be seen that both PAA and PA3 have a decreasing trend of water retention with prolonging the time: about 88 and 87% of distilled water for PA3 and PAA, respectively, maintained at 60C after 5.5 h of water-retention test. Moreover, for a given duration of time the

Figure 7 TGA curves of (a) crosslinked PAA and (b) PA3 at a heating rate of 10C/min.

of crosslinked PAA started at 360C (21.7%), whereas PA3 has a major weight loss starting at 382C (29.2%). Therefore, crosslinked PAA and PA3 have initial decomposition temperatures of 360 and 382C, respectively. The results also indicated that introduction of attapulgite to the polymer network results in an increase in thermal stability. SEM observations The micrographs of uncrosslinked PAA, crosslinked PAA, and PA3 are shown in Figure 8(a), (b), and (c), respectively. The SEM micrograph of uncrosslinked PAA, which is water-soluble and has no absorbency, is shown to be nonporous [Fig. 8(a)], whereas the SEM micrographs of crosslinked PAA and PA3, which have good water absorbency, show the samples to be microporous. In addition, PA3 has a greater absorbency and shows a broad network structure [Fig. 8(c)], whereas crosslinked PAA has a ne network structure [Fig. 8(b)]. These observations are in good agreement with our water-absorbency observations. Water-retention test Water retention of the swollen superabsorbent composites was determined by a heating oven test at 60 or 100C and centrifuging the samples at 4000 rpm for 30 min. Water-retention values of the swollen superabsorbent composite samples and the swollen PAA sample are presented in Table II. From Table II we can see that all swollen superabsorbent composite samples show good water-retention ability and can retain approximately 97% of the distilled water after centrifugation at 4000 rpm for 30 min. Figure 9 shows the water-retention capacity of swollen superabsorbent composite and crosslinked PAA at

Figure 8 Scanning electron micrographs of (a) uncrosslinked PAA, (b) crosslinked PAA, and (c) PA3.

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TABLE II Water Retention for the Swollen Samples of Superabsorbent Composite and Crosslinked PAA
Sample PAA Water retention (%) 95.4 PA1 98.5 PA2 96.8 PA3 98.4 PA4 97.5

water retention of the PA3 sample is slightly better than that of PAA. In the 100C water-retention test, the water loss of PA3 reached almost 96.2%, whereas PAA had a water loss of 60.4% after the 5.5-h water-retention test. According to a previous study,21 the water in a hydrogel can be classied into bound water, halfbound water, and free water. Compared to bound water and half-bound water, the free water in a hydrogel has high mobility and can easily be lost. The number of hydrophilic groups (COOH and COONa) in a unit volume in superabsorbent composite is smaller than that in PAA, so the percentages of bound water and half-bound water content in swollen PAA are higher than those in swollen PA3; that is, swollen PA3 has a higher percentage of free water content than that of swollen PAA. As a result, PAA has a better water-retention ability than PA3 under higher temperature. After the swollen superabsorbent composite thoroughly loses its absorbed water, the resulting dry sample still retains a good water-absorbing ability. It can be seen from Figure 10 that PA3 still retains approximately 85% of its initial water absorbency (initial water absorbency of PA3; see Table I), even after repeating the swelling deswellingswelling test ve times (the heating oven test repeated ve times at

Figure 10 Water absorbency of PA3 as a function of swelling deswellingswelling times.

100C). These superabsorbent composites may prove useful in recyclable superabsorbent materials. CONCLUSIONS Novel superabsorbent composites of crosslinked poly(acrylic acid)/attapulgite were prepared in an aqueous solution by graft copolymerization reaction of acrylic acid on attapulgite micropowder using N,Nmethylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator. These crosslinked superabsorbent compsites were characterized by TGA and SEM. The graft copolymerization reaction of acrylic acid on attapulgite micropowder was characterized by IR. The effects of initial monomer concentration, reaction temperature, degree of neutralization, amount of crosslinker, initiator, and attapulgite on the water absorbency of superabsorbent composites were investigated. Under our experimental conditions, a crosslinked poly(acrylic acid)/attapulgite superabsorbent composite with a water absorbency greater than 1000 g H2O/g was synthesized, which has a composition of 0.2 wt % of crosslinker, 1.0 wt % of initiator, 10 wt % of attapulgite, a neutralization degree of 60%, and a reaction temperature of 70C. It was also found that crosslinked poly(acrylic acid)/attapulgite superabsorbent composite is characterized by good water retention under load. This excellent water absorbency and water retention under load may be especially useful in agricultural and horticultural applications. References
1. Yoshida, M.; Asano, M.; Suakura, M. Eur Polym Mater 1989, 25, 1197. 2. Shiga, T.; Hirose, Y.; Okada, A.; Kurauchi, T. J Appl Polym Sci 1992, 44, 249.

Figure 9 Water retention of swollen samples as a function of time at 60 and 100C.

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3. Shiga, T.; Hirose, Y.; Okada, A.; Kurauchi, T. J Appl Polym Sci 1993, 47, 113. 4. Shimomura, T.; Namba, T. In: Superabsorbent Polymers; Buchholz, F. L.; Peppas, N. A., Eds.; ACS Symposium Series 573; American Chemical Society: Washington, DC, 1994. 5. Tsuji, S.; Musika, H.; Itoh, M.; Saga, J.; Fujiwara, T.; Hatsuda, T. Eur. Pat. 356,161, 1990. 6. Harper, B. G.; Bashaw, R. N.; Atkins, B. L. U.S. Pat. 3,669,103, 1972. 7. Tsubakimoto, T.; Shimomura, T.; Kobabyashi, H. Jpn. Pat. 62,149,335, 1987. 8. Ende, M.; Hariharan, D.; Pappas, N. A. React Polym 1995, 25, 127. 9. Zhu, X. L.; Gu, M.; Zhao, F. Polym Mater Sci Eng 1994, 5, 56 (in Chinese). 10. Wu, J. H.; Lin, J. M.; Zhou, M.; Wei, C. R. Macromol Rapid Commun 2000, 21, 1032.

11. Lin, J. M.; Wu, J. H.; Yang, Z. F.; Pu, M. L. Macromol Rapid Commun 2001, 22, 422. 12. Baker, J. P.; Hong, L. H.; Blanch, H. W.; Pransnitz, J. M. Macromolecules 1992, 27, 1446. 13. Lee, W. F.; Yeh, P. L. J Appl Polym Sci 1997, 64, 2371. 14. Chen, J. W.; Zhao, Y. M. J Appl Polym Sci 2000, 75, 808. 15. Chen, J. W.; Zhao, Y. M. J Appl Polym Sci 1999, 74, 119. 16. Flory, P. J. Principles of Polymer Chemistry; Cornell University Press: Ithaca, NY, 1953. 17. Allcock, H. R.; Frederick, W. L. Contemporary Polymer Chemistry; Prentice-Hall: Englewood Cliffs, NJ, 1981. 18. Liu, Z. S.; Remple, G. L. J Appl Polym Sci 1997, 64, 1345. 19. Song, Y.; Cui, Z.; Chen, X. Yingyong Huaxue 1995, 12, 117. 20. Panduranga Rao, K.; Kanniappan, E. P.; Jayaraman, K. S.; Thomas, J. K.; Nayudamma, Y. J Appl Polym Sci 1981, 26, 3343. 21. Aisawa, I. Bull Chem Soc Jpn 1967, 44, 2967.

European Polymer Journal 41 (2005) 16301637

EUROPEAN POLYMER JOURNAL

www.elsevier.com/locate/europolj

Synthesis and properties of clay-based superabsorbent composite

An Li, Aiqin Wang
*
Centre for Ecological and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China Received 13 August 2004; received in revised form 10 October 2004; accepted 30 January 2005 Available online 8 March 2005

Abstract A novel superabsorbent composites based on acrylic acid, acrylamide, and inorganic clay mineral-attapulgite were synthesized through a solution polymerization to improve water and saline absorbencies. The superabsorbent composite was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The eects of saline solutions, amount of initiator, crosslinker and attapulgite on the water absorbency of superabsorbent composites were investigated. The water retention test of superabsorbent composites were also carried out. The superabsorbent composite exhibited improved water and saline absorbencies compared with that of crosslinked poly(acrylic acidco-acrylamide) superabsorbent polymer. The water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% reaches more than 1400 g H2O/g and 110 g H2O/g in distilled water and 0.9% NaCl solution, respectively. 2005 Elsevier Ltd. All rights reserved.
Keywords: Acrylic acid; Acrylamide; Attapulgite; Superabsorbent composite; Water absorbency

1. Introduction Superabsorbent polymers are loosely crosslinked networks that can absorb a large amount of water in a short time and retain water under pressure. Although superabsorbent polymers have been abundantly used in the disposable diaper industry for the past 30 year, their applications are still being expanded to many elds including agriculture and horticulture [1,2], sealing composites [3], articial snow [4,5], drilling uid additives [6], medicine for drug delivery system [79] and so on.

* Corresponding author. Tel.: +86 931 4968118; fax: +86 931 8277088. E-mail address: aqwang@ns.lzb.ac.cn (A. Wang).

Recently, the preparation of polymer/clay superabsorbent composites has received great attention because of their relative low production cost and high water absorbency [10,11]. The preparation and the swelling behaviors of poly(acrylic acid)/attapulgite superabsorbent composite have been reported in our previous study [12,13]. In which, we know that the water absorbency of the poly (acrylic acid)/attapulgite superabsorbent composite in distilled water was greatly improved as compared with crosslinked poly (acrylic acid) superabsorbent polymer, but the water absorbing ability of superabsorbent composite in saline solutions only slightly increased. It is well known that the water absorbing ability of a superabsorbent in saline solution is also very important for many applications. Therefore, the synthesis of new superabsorbent composite which has

0014-3057/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2005.01.028

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high water absorbency both in distilled water and saline solution and developing their applications still represent interesting research areas. Acrylamide is a kind of nonionic monomer and has great advantage on its good salt-resistant performance as a raw material for superabsorbent. Attapulgite, as a good substrate for superabsorbent composite materials, is a layered aluminium silicate with reactive groups OH on the surface. In order to reduce costs and improve the comprehensive waterabsorbing properties of the superabsorbent materials, to graft acrylic acid and acrylamide copolymer onto attapulgite and fabricate a composite consisting of polymer and attapulgite micropowder can be a priority. In this paper, we report the synthesis of superabsorbent composites by graft copoly- merization reaction of acylic acid (AA) and acrylamide (AM) on attapulgite micropowder using N,N-methylene-bisacrylamide (MBA) as a crosslinker and ammonium persulphate (APS) as an initiator in an aqueous solution. Aspects investigated included the optimum synthesizing conditions.

Fig. 1. Schematic structure of attapulgite.

2. Experimental 2.1. Materials Acrylic acid (AA, chemically pure, Shanghai Wulian Chemical Factory, Shanghai, China) was distilled under reduced pressure before use. Acrylamide (AM, chemically pure, Shanghai Chemical Reagent Factory, Shanghai, China) was used as purchased. Ammonium persulfate (APS, analytical grade, Xian Chemical Reagent Factory, Xian, China) was recrystallized from water. N,N-methylenebisacrylamide (MBA, chemically pure, Shanghai Chemical Reagent Factory, Shanghai, China) was used as purchased. Attapulgite micropowder, (Xuyi Colloidal Co., Ltd, Jiangsu, China), milled through 320-mesh screen, followed by treatment with 37% hydrochloric acid for 48 h and washed with distilled water until pH 7 to remove any residual hydrochloric acid, was dried at 105 C for 8 h prior to use. All solutions were prepared with distilled water. The schematic illustration (Fig. 1) of attapulgite is presented as below: 2.2. Preparation of superabsorbent composites A series of the samples with dierent amounts of attapulgite, crosslinker, initiator and acrylic acid with dierent degrees of neutralization were prepared by the following procedure: Typically, acrylic acid (4.2 g) was dissolved in 15 ml distilled water and then neutralized with 4.6 ml of sodium hydroxide solution (5 M) in a four-neck ask equipped with a stirrer, condenser, thermometer, and nitrogen line. attapulgite power (0.72 g) and acrylamide (2.13 g) were added to the above partial neutralized monomer solution. Under a nitrogen atmo-

sphere, the crosslinker MBA (14.3 mg) was added to the AA-AM-attapulgite mixture solution and the mixed solution was stirred at room temperature for 30 min. The water bath was heated slowly to 70 C with eective stirring after radical initiator APS (71.3 mg) was introduced to the mixed solution. After 3 h of the reaction, the resulting product was washed several times with distilled water, dried at 70 C to a constant weight, then milled and screened. All samples were used had a particle size in the range of 4080 mesh. 2.3. Preparation of crosslinked poly(acrylic acidcoacrylamide) superabsorbent polymer The procedure of preparation of crosslinked poly (acrylic acid-co-acrylamide) superabsorbent polymer is similar to that of preparation of superabsorbent composite except attapulgite is omitted. 2.4. Water absorbency measurement A weighted quantity of the superabsorbent composite was immersed in distilled water or saline solutions at room temperature to reach the swelling equilibrium. Swollen samples were then separated from unabsorbed water by ltered over a 100-mesh screen. The water absorbency (QH2 O ) of superabsorbent composite was determined by weighing the swelled samples, and the QH2 O of the samples was calculated using the following equation: QH2 O m2 m1 =m1 1

where m1 and m2 are the weights of the dry sample and the water-swollen sample, respectively. QH2 O was calculated as grams of water per gram of sample. 2.5. Characterization The IR spectra of the superabsorbent composite were recorded on a FTIR (Thermo Nicolet, NEXUS, TM) using KBr pellets. Thermal stability studies of dry

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A. Li, A. Wang / European Polymer Journal 41 (2005) 16301637

samples were performed on a Perkin-Elmer TGA-7 thermogravimetric analyzer (Perkin Elmer Cetus Instruments, Norwalk, CT), with a temperature range of 25 700 C at a heating rate of 10 C/min using a dry nitrogen purge at a ow rate of 50 ml/min. The morphology of the dried samples was examined using a JSM-5600LV SEM instrument (JEOL, LTD) after coating the sample with gold lm.

3. Results and discussion 3.1. Eect of initiator content Fig. 2 shows the eect of the initiator content on the water absorbency of superabsorbent composite. The water absorbency increases as APS content rises from 0.2% to 1.0% and decreases with further increase in the content of APS. The relation between the average kinetic chain length (V) and concentration of the initiator in free-radical polymerization is given by the following equation [14]: V 1=2k p fk i k t
1=2

mer chain ends do not contribute to the water absorbency. Therefore, this is responsible for the decrease in the water absorbency with increase of the initiator content. When the content of APS is below the optimum values, the swelling capacity of superabsorbent composite is also decreased. This may due to a decrease in the number of radicals produced as the content of APS decreases. The network cannot be formed eciently with a few numbers of radicals in free-radical polymerization reaction, which results in the decrease of the water absorbency [12]. 3.2. Eect of crosslinker content The eect of crosslinker content on water absorbency is shown in Fig. 3. It can be seen from Fig. 3 that the water absorbency decreases with the increase of crosslinker content from 0.2% to 1.0%. The relation between the swelling ratio and network structure parameter for the swelling of ionic network was given by Flory [16], usually used as the following two equivalent equation:
=3 1=2 2 Q5 1=2 X 1 =V 1 =V e =V 0 m i=2V u S =3 1=2 2 Q5 1=2 X 1 =V 1 M c =qp m i=2V u S

1=2

2 1 2M c =M n 1 4

where kp, ki and kt are the rate constants for propagation, initiator, and termination, respectively; f, the eciency of initiation by the initiator; and [I] and [M], the initial concentration of the initiator and monomer, respectively. According to Eq. (2), the molecular weight in free-radical polymerization decreases with increase of the initiator concentration. With decrease of the molecular weight, the relative amount of polymer chain ends increase. As mentioned in previous study [15], the poly-

where Qm is swelling ratio; i/Vu, the concentration of xed charge referred to the unswollen network; S, the ionic concentration in the external solution; (1/2 X1)/V1, the anity of the hydrogel with water;Ve/V0, the crosslinked density which refers to the number of eectively crosslinked chains in unit volume; Mc, the average

1600
1400

1400

Water Absorbency (g/g)

1000

Water Absorbency (g/g)

1200

1200 1000 800 600 400

800

600

400

200
200 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

0.2

0.4

0.6

0.8

1.0

APS Content (wt%)

MBA Content (wt%)

Fig. 2. Eect of initiator content on water absorbency of superabsorbent composite in distilled water: reaction temperature, 70 C; 40% neutralization degree of AA; molar ratio of AM to AA is 0.51, weight ratio of crosslinker and attapulgite in the feed is 0.2% and 10%, respectively.

Fig. 3. Eect of crosslinker content on water absorbency of superabsorbent composite in distilled water:reaction temperature, 70 C; 40% neutralization degree of AA; molar ratio of AM to AA is 0.51, weight ratio of initiator and attapulgite in the feed is 1.0% and 10%, respectively.

A. Li, A. Wang / European Polymer Journal 41 (2005) 16301637

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molecular weight of the network chains; qp, the density of the polymer, and Mn, the average molecular weight of the polymer before crosslinking. According to Eq. (3), the swelling ratio of the hydrogel has a relation to the ionic osmotic pressure, crosslinked density, and anity of the hydrogel with water. When the crosslinker content increased, the crosslinking density of the superabsorbent composite also increased. This would result in a decrease in the space between the copolymer chain and lead a decrease in water absorbency. When crosslinker content is lower than 0.2%, the absorbency of superabsorbent composite is diminished because of an increase of soluble material. The results are in conformity with Florys network theory and similar observations have been reported by others [17,18]. 3.3. Eect of molar ratio of AM to AA Fig. 4 shows the eect of the molar ratio of AM to AA on water absorbency of superabsorbent composite. The water absorbency decreases with the increase of the molar ratio of AM to AA in a feed ratio range of 0.511.03. However, inverse result was observed when the molar ratio of AM to AA is below 0.51. Similar results were observed in the study of crosslinked acrylic acid and acrylamide copolymers [15]. There are three kinds of hydrophilic groups (CONH, COONa and COOH groups) in the polymer chains of the composite network. As reported in previous study [19], the collaborative absorbent eect of CONH, COONa and COOH groups is superior to that of single CONH, COONa or COOH group. When the CONH, COONa and COOH groups on the composite cooperate in suitable

ratio, the repelling action between ions will reduce and the higher water absorbent ability will produce. Under our experimental conditions, the molar ratio of AM to AA in a feed ratio range of 0.51 possesses the highest water absorbency. 3.4. Eect of attapulgite content Table 1 shows the eect of attapulgite content on the water absorbency. The water absorbency decreases with the increase of attapulgite content. As described in previous study [1012], the inorganic clay mineral particle in network acts as an additional network point. The crosslinking density of superabsorbent composite increases with the increase of attapulgite content, which results in a decrease in water absorbency. It also can be seen from Table 1 that the superabsorbent composites show high waterabsorbing capacity in both distilled water and 0.9% NaCl solution as compared with PAAM, especially when the superabsorbent composite contains low percentage of attapulgite (for example PAAM1). The mechanism of PAA grafting onto attapulgite was reported in our previous study [12]. It was presumed by a similar mechanism that the hydroxyl group present in the attapulgite may react with the APS and liberate a free radical on the attapulgite structure and graft polymerization will take place on these free radicals giving poly (acrylic acid-co-acrylamide) (or partial PAA and PAM) branches on the attapulgite backbone. It should be noted that the presence of initiator in the polymerization system leads not only to grafting but also to the initiation of homopolymerization. The homopolymers of PAA and PAM are soluble in the medium of reaction (water) and would be ltered o during ltration. However, in the presence of crosslinker with such a high percentage of 0.2%, the homopolymers can not be extracted completely from the reaction mixture. In addition, These

1400

Water Absorbency (g/g)

1200

1000

Table 1 Eect of amount of attapulgite on water absorbency of the superabsorbent composites Sample no. Attapulgite percentage (wt.%) QH2 O (g/g) Distilled water PAAM PAAM1 PAAM2 PAAM3 PAAM4 0 10 20 30 40 684 1414 960 800 691 0.9 wt.% NaCl 72 117 94 82 70

800

600

400

0.2

0.4

0.6

0.8

1.0

Molar Ratio of AM to AA

Fig. 4. Eect of molar ratio of AM to AA content on water absorbency of superabsorbent composite in distilled water: reaction temperature, 70 C; 40% neutralization degree of AA; weight ratio of crosslinker, initiator and attapulgite in the feed is 0.2%, 1.0% and 10%, respectively.

Reaction conditions: reaction temperature, 70 C; 40% neutralization degree; molar ratio of AM to AA is 0.51, weight ratio of crosslinker and initiator in the feed is 0.2% and 1.0%, respectively.

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A. Li, A. Wang / European Polymer Journal 41 (2005) 16301637

Fig. 5. Infrared spectra of superabsorbent composite (a), PAAM (b) and attapulgite (c).

homopolymers would also be crosslinked and form the network. Since the residual homopolymers in network would help in enhancing the water absorbency of nal product, no attempt was made to extract the homopolymers from the superabsorbent composite. 3.5. Infrared spectra The infrared spectra of superabsorbent composite PAAM1, PAAM and attapulgite are shown in Fig. 5(a)(c), respectively. According to the IR spectra of PAAM1, The peaks observed were at 3447 cm1, corresponding to the NH stretching of acrylamide unit, 2950 cm1, corresponding to the CH stretching of acrylate unite, 1721 cm1, corresponding to the tC@O of acrylate unit, 1667 cm1, corresponding to the carbonyl moiety of the acrylamide unit, 1175 cm1, corresponding to the COO stretching of acrylate unit, 1031 cm1, corresponding to the SiO stretching of attapulgite. The infrared analysis result of superabsorbent composite in Fig. 5(a) shows that all characteristic groups, i.e., COOH (or COONa), CONH, CH, and SiO, exist in product. In addition, by compared with Fig. 5(a) and (c), the absorption peaks at 3621cm1 and 3549cm1 attributed to the OH groups on attapulgite (Fig. 5(c)) disappeared after reaction (Fig. 5(a)), it is suggested that the graft copolymerization between OH groups on attapulgite and monomers take place during the reaction. 3.6. Thermal stability The thermogravimetic analysis (TGA) of PAAM and PAAM1 are shown in Fig. 6. Both PAAM and PAAM1 show a very small weight loss below 100 C, implying a loss of moisture. At around 345 C, PAAM and PAAM1 have similar signicant weight losses of 19.3% (342 C)
Weight (%)

100

PAAM1 PAAM

80

60

40

20 100 200 300 400 500 600 700

Temperature (oC)

Fig. 6. TGA curves of PAAM1 and PAAM at a heating rate of 10 C/min.

and 20.1% (348 C), respectively. The major weight loss of PAAM started at 460 C (54.4%) whereas PAAM1 has a major weight loss started at 505 C (62.5%). Therefore, PAAM and PAAM1 has a decomposition temperature of 460 C and 505 C, respectively. The results indicated that the introduction of attapulgite to polymer network results in an increase in thermal stability. This phenomenon may be due to the fact that the attapulgite micro-particles in network can act as a heat barrier, which enhances the overall thermal stability of the composite. 3.7. SEM observations The micrographs of PAAM and PAAM1 are shown in Fig. 7(a) and (b), respectively. The sample shows a ne network structure and nonporous appears on the

A. Li, A. Wang / European Polymer Journal 41 (2005) 16301637

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Fig. 7. Scanning electron micrographs of (a) PAAM and (b) PAAM1.

SEM of PAAM, while on the SEM of PAAM1, which has better water absorbency than that of PAAM, the samples is microporous and shows a broad network structure. These observations are in good agreement with our water absorbency observations (see Table 1). 3.8. Eect of saline solution on water absorbency Fig. 8 shows the eect of saline solutions (NaCl(aq); MgCl2(aq); CaCl2(aq) and FeCl3(aq)) on water absorbency of superabsorbent composite. As shown in Fig. 8, the water absorbency decreases with the increase of the concentration of all four salt solutions. The eect of the ionic strength of the external solution on the swelling has been determined using the following relation suggested by Hermans [20]:
=3 2 Q5 eq A Bi =I

ionic strength of the external solution, and A and B are empirical parameters. According to the Eq. (5), the water absorbency of superabsorbent decreases with increase of ionic strength of external solution. This decrease in water absorbency with increasing ionic strength may be attributed to the decrease in the osmotic pressure dierence between the superabsorbent composite and the external saline solution. This also can be seen from Fig. 8 that for a given concentration of salt solution, the water absorbency in NaCl solution is far higher than that of in MgCl2, CaCl2 and FeCl3 solutions. This dramatic decrease of water absorbency in multivalent cationic solutions may be due to the fact that the complexing ability of the carboxylate groups inducing the formation of intramolecular and intermolecular complexes which result in an increase in the crosslink density of network [13,21]. 3.9. Swelling rate The swelling rate of superabsorbent composite was determined and is shown in Fig. 9. It is indicated that the swelling rate of superabsorbent composite is high in 030 min and the water absorbency of superabsorbent composite reaches 1135 g/g within 30 min. After 30 min, the swelling rate becomes low and the maximum swelling capacity of superabsorbent composite was reached within 60 min. 3.10. Water retention test Water retention of the swollen PAAM and superabsorbent composites was determined by centrifuging it at 4000 rpm for 30 min. It can be seen from Table 2 that the swollen superabsorbent composite samples show good ability of water retention and can keep approximately 96% of the distilled water. After the swollen sample thoroughly lost its adsorption water, the resulting dry sample (PAAM1) still retains good water absorbing ability and can keep approximately 84% of initial water absorbency even after repeating 5 times of heating oven

where Qeq is the water absorbency at equilibrium; i, the concentration of the charges bound to the gel; I, the

180 160

Water absorbency (g/g)

140 120 100 80 60 40 20 0 0.0 0.2 0.4 0.6

NaCl MgCl2 CaCl2 FeCl3

0.8

1.0

Concentration of saline solution (wt%)

Fig. 8. Water absorbency of PAAM1 in NaCl, MgCl2, CaCl2 and FeCl3 aqueous solutions with various concentrations.

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A. Li, A. Wang / European Polymer Journal 41 (2005) 16301637

4. Conclusion Novel poly (acrylic acid-co-acrylamide)/attapulgite superabsorbent composites were synthesized by graft copolymerization reaction of acylic acid and acrylamide on attapulgite micropowder using N,N-methylene-bisacrylamide as a crosslinker and ammonium persulphate as an initiator in aqueous solution. Under our experimental conditions, a crosslinked poly(acrylic acid-coacrylamide)/attapulgite superabsorbent composite with a water absorbency of higher than 1400 g H2O/g was synthesized having a composition of 0.2% crosslinker, 1.0% initiator and 10% attapulgite. The water retention test of superabsorbent composites were also carried out and results obtained from this study show that the superabsorbent composite have a good water retention capacity. As a novel superabsorbent composite material, the water absorbencies in distilled water and in 0.9% NaCl solution were both improved and the production cost was signicant reduced by compared with crosslinked poly (acrylic acid-co-acrylamide) superabsorbent polymer. This excellent water absorbency and water retention under load may prove especially practical in agricultural and horticultural applications.

Water absorbency (g/g)

20

40

60

80

100

Time (min)

Fig. 9. Water absorbency of PAAM1 as a function of time.

Table 2 Water retention for the swollen samples of superabsorbent composite and crosslinked PAAM Sample PAAM PAAM1 97.2 PAAM2 96.4 PAAM3 96.1 PAAM4 95.8

Water 95.4 retention (%)

Acknowledgement This work was nancially supported by the Western Action Project of CAS (No. KGCXZ-SW-502) and the 863 major project of the Ministry of Science and Technology, P. R. China (No. 2002AA6Z0310071).

test at 100 C (the results are presented in Fig. 10), whereas only approximately 68% initial water absorbency can be kept for the resulting dry sample of PAAM (initial water absorbency of PAAM1 and PAAM see Table 1). Results obtained from this study show that the superabsorbent composites have a good water retention capacity. These superabsorbent composites may prove useful in recyclable superabsorbent materials.

References
[1] Yao KJ, Zhou WJ. J Appl Polym Sci 1994;53:15338. [2] Zhou WJ, Yao KJ, Kurth MJ. J Appl Polym Sci 1996;62:9115. [3] Tsubakimoto T, Shimomura T, Kobabyashi H. Jpn Patent 1987;62,149,335. [4] Miura Y, Hirano K, Nate T, Kambayashi T, Ohtsuka M, Nagai T. Eur Patent 1991;440,256. [5] Tanaka H, Kambayashi T, Sugiyama Y, Nagai T, Nagata K, Kubota K, Hirano K. Eur Patent 1992;501,482. [6] Walker CO. US Patent 1987;4(664):816. [7] Colombo P. Adv Drug Delivery Rev 1993;11:3757. [8] Dong LC, Homan AS. J Control Release 1991;15:14152. [9] Ende M, Hariharan D, Pappas NA. React Polym 1995;25:12737. [10] Wu JH, Lin JM, Zhou M, Wei CR. Macromol Rapid Commun 2000;21:10324. [11] Lin JM, Wu JH, Yang ZF, Pu ML. Macromol Rapid Commun 2001;22:4224. [12] Li A, Wang AQ, Chen JM. J Appl Polym Sci 2004;92:1596603. [13] Li A, Wang AQ, Chen JM. J Appl Polym Sci 2004;94:186976.

1400 1200

PAAM1 PAAM

Water Absorbency (g/g)

1000 800 600 400 200 0

Swelling-deswelling-swelling Times

Fig. 10. Water absorbency of PAAM1 as a function of swellingdeswellingswelling times.

A. Li, A. Wang / European Polymer Journal 41 (2005) 16301637 [14] Allcock HR, Frederick WL. Contemporary polymer chemistry. Englewood, Clis, NJ: Prentice-Hall; 1981. [15] Liu ZS, Remple GL. J Appl Polym Sci 1997;64:1345 53. [16] Flory PJ. Principle of polymer chemistry. Ithaca, NY: Cornell University Press; 1953. [17] Chen JW, Zhao YM. J Appl Polym Sci 1999;74:11924.

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[18] Chen JW, Zhao YM. J Appl Polym Sci 2000;75:80814. [19] Wu JH, Wei YL, Lin JM, Lin SB. Polymer 2003;44:651320. [20] Hermans JJ. Flow properties of disperse system. New York: Wiley-Interscience; 1953. p. 61. [21] Castal D, Ricard A, Audebert R. J Appl Polym Sci 1990;39:1129.

European Polymer Journal 41 (2005) 24342442

EUROPEAN POLYMER JOURNAL

www.elsevier.com/locate/europolj

Study on superabsorbent composite. III. Swelling behaviors of polyacrylamide/attapulgite composite based on acidied attapulgite and organo-attapulgite
Junping Zhang
a

a,b

, Hao Chen

a,b

, Aiqin Wang

a,*

Center of Ecological and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China b Graduate School of the Chinese Academy of Sciences, Beijing 100049, PR China Received 15 November 2004; received in revised form 14 March 2005; accepted 31 March 2005 Available online 21 July 2005

Abstract A novel kind of salt-resistant superabsorbent composite, polyacrylamide/attapulgite, from acrylamide (AM) and attapulgite (APT) was prepared by free-radical aqueous polymerization, using N,N 0 -methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The organication of APT with hexadecyltrimethyl ammonium bromide (HDTMABr) was proved by FTIR and XRD. The eects of acidied APT (H+-APT), organoAPT (HDTMABr-APT) and the content of APT in the superabsorbent composite on the water absorbency and the initial swelling rate for the superabsorbent composite in distilled water and in various saline solutions were studied. The eects of incorporated HDTMABr-APT and H+-APT on the reswelling ability of the superabsorbent composites were investigated. The results indicate that the incorporation of APT had remarkable inuence on the improvement of water absorbency and swelling rate of the composites. Comparing with the composite doped with H+-APT, the water absorbency for the composite doped with 10 wt% HDTMABr-APT was enhanced from 2140 g g1 to 2800 g g1 in distilled water and from 100 g g1 to 121 g g1 in 0.9 wt% NaCl solution, respectively. The water absorbency of the composites in various saline solutions decreased with the increasing concentration, especially for the multivalent cations. In addition, the reswelling ability of the superabsorbent composites is also improved evidently by adding a small amount of HDTMABr-APT into the composite, comparing with that of incorporated with H+-APT. 2005 Elsevier Ltd. All rights reserved.
Keywords: Attapulgite; Superabsorbent; Composites; Water absorbency; Swelling

1. Introduction Superabsorbents are slightly crosslinked hydrophilic polymers that can absorb, swell and retain aqueous uids up to thousands of times their own weight. Since the rst superabsorbent was reported by the US Department of agriculture in 1961 [1], many eorts has been made to modify their swelling capability, swelling rate and

* Corresponding author. Tel.: +86 931 4968118; fax: +86 931 8277088. E-mail address: aqwang@lzb.ac.cn (A. Wang).

0014-3057/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2005.03.022

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swollen gel strength [26], and they are widely used in many elds, such as hygienic products [7], horticulture [8], sealing [9], drug-delivery systems [1012] and coal dewatering [13], because of their superior characters to traditional absorbents (such as sponge, cotton and pulp, etc.). Much attention has been paid to inorganic materials recently for the preparation of superabsorbent polymeric gels, such as kaolin [14], montmorillonite [15,16], attapulgite [12], mica [17], bentonite and sercite [18]. The incorporation of these mineral powders can not only reduce production cost, but also improve the properties (such as swelling ability, gel strength, mechanical and thermal stability) of superabsorbents and accelerate the generation of new materials for special applications [19]. Polymer/layered silicate nanocomposites frequently exhibit remarkably improved mechanical and materials properties (such as a higher modulus, increased strength and heat resistance, decreased gas permeability and ammability, and increased biodegradability of biodegradable polymers) and are attracting considerable interest in polymer science research [20]. Attapulgite, a kind of hydrated octahedral layered magnesium aluminum silicate absorbent mineral with reactive OH groups on its surface, is less sensitive to salts comparing with other clays (such as smectite) [21]. As an extension of our previous work on attapulgite based superabsorbent composites [12,22], the organo-APT was introduced into the PAM system to study the inuences of APT on the comprehensive swelling behaviors of the superabsorbent composite.

HDTMABr (0.44 g) anhydrous alcohol solution. The suspension was stirred vigorously at 80 C for 8 h, and then HDTMABr-APT was formed. The separated HDTMABr-APT was washed with large volume of anhydrous alcohol to remove excess HDTMABr, and then dried in an oven at 70 C for 6 h until the weight was constant. 2.3. Preparation of the superabsorbent composites A series of APT micropowder based superabsorbent composites with dierent amount of APT were synthesized according to the following procedure. The crosslinker, MBA (10.3 mg), and AM monomer (7.10 g) were introduced into a 250 ml four-neck ask, equipped with a stirrer, a reux condenser, a thermometer and a nitrogen line. The mixture was stirred until the MBA was dissolved completely, and then appropriate amount of H+-APT or HDTMABr-APT was dispersed in the mixed solution. After being purged with nitrogen for 30 min to remove the oxygen dissolved in the solution, the mixed solution was heated to 40 C gradually, and then the initiator, APS (40.5 mg), was introduced into the ask. The solution was stirred vigorously and a nitrogen atmosphere was maintained all through the polymerization of 3 h, and then 30.0 ml of sodium hydroxide solution (2 mol l1) was added and the primary product was heated to approximately 95 C to be saponied for 2 h. After saponication, the product was immersed in excess distilled water and then ltered for several times to remove any unreacted reactants until pH 7 was achieved. The depurative product was dried in an oven at 70 C until the weight of the product was constant and an ashen polymer was obtained. The product was milled and all samples used for test had a particle size in the range of 4080 mesh. 2.4. Measurement of water absorbency and swelling rate A weighted quantity of the superabsorbent composite (0.05 g) powder was immersed in excess distilled water (500 ml) at room temperature for 4 h to reach swelling equilibrium. Swollen samples were then separated from unabsorbed water by ltering through a 100-mesh screen. The water absorbency of the superabsorbent composite, QH2 O , was calculated using the following equation: QH2 O m2 m1 m1 1

2. Experimental 2.1. Materials Acrylamide (analytical grade, supplied by Shanghai Chemical Factory, Shanghai, China) was puried by method as reported [23]. Ammonium persulfate as an initiator was supplied by Xian Chemical Reagent Factory (Xian, China), and N,N 0 -methylenebisacrylamide as a crosslinker was obtained from Shanghai Chemical Reagent Corp. (Shanghai, China). Hexadecyltrimethyl ammonium bromide, purchased from Beijing Chemical Reagent Factory, was used directly as received. Attapulgite micropowder, supplied by Linze Colloidal Co. (Gansu, China), was milled through a 250-mesh screen and treated with 37% hydrochloric acid for 72 h, followed by washing with distilled water until pH 6 was achieved, and then the H+-APT was obtained. Other agents used were all analytical grade and all solutions were prepared with distilled water. 2.2. Preparation of organo-APT HDTMABr-exchanged APT was prepared as follows: 4.0 g H+-APT was suspended in 40 ml

where m1 and m2 are the weights of the dry sample and the swollen sample, respectively. QH2 O is calculated as grams of water per gram of sample. Swelling rate of the superabsorbent composite was measured according to the previously reported method [24].

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J. Zhang et al. / European Polymer Journal 41 (2005) 24342442

2.5. Absorbency in various saline solutions 0.10 g superabsorbent composite was immersed in 250 ml of various saline solutions with dierent concentrations (NaCl(aq), MgCl2(aq), CaCl2(aq), FeCl3(aq)) for 4 h to maintain equilibrium. The swollen samples was ltered through a 100-mesh screen and weighted. The effects of various saline solutions on saturated absorbency can then be obtained. 2.6. Reswelling ability The specimen (0.05 g) was immersed in certain milliliter of water to ensure the swelling equilibrium was achieved. The swollen gel was placed in an oven at 100 C until the gel was dried thoroughly. Equal milliliter of water was added to the dried gel and placed in the oven again. Similar procedure was repeated and then saturated absorbency of the sample after several times of re-swelling were obtained. 2.7. Characterization FTIR spectra of samples were taken as KBr pellets using a Thermo Nicolet NEXUS TM spectrophotometer. Power XRD analyses of the specimens were performed using an X-ray power diractometer with Cu anode (PAN alytical Co. Xpert PRO), running at 40 kV and 30 mA, scanning from 3 to 15 at 3/min.

3.2. X-ray diraction analysis The organication of APT clay is also analysed by X-ray powder diraction (XRD) and the powder patterns of APT, HDTMABr-APT and PAM/HDTMABr-APT composite are presented in Fig. 3. A typical diraction peak of APT at 8.50, which corresponds to a basal , is evident according to Fig. 3(a). spacing of 10.40 A After organication with HDTMABr, this peak is at 8.47 corresponding to a basal spacing of 10.48 A (Fig. 3(b)). According to the results of XRD and FTIR, it can be concluded that HDTMABr is just adsorbed on the surface of APT during the cation-exchange process without destroying the crystalline structure of it. The diraction peak of the HDTMABr-APT is still here at 8.44 in the powder XRD pattern of the amorphous composite (Fig. 3(c)). This indicated that the interaction of AM and HDTMABr-APT during polymerization also occurred on the surface of HDTMABr-APT microparticles without intercalating into the stacked silicate galleries. The suitable range of cation exchange capacity (CEC) for clays, which can be intercalated, is 60 120 mmol/100 g [26]. However, the CEC of attapulgite is in the range of 3040 mmol/100 g [27]. So, it may be the main reason for the unsuccessful intercalation. 3.3. Eect of APT content on water absorbency of the superabsorbent composites The type and the amount of APT are important factors inuencing the water absorbency of the superabsorbent composite, since it is the reaction between OH group of APT and ethenyl of AM that forms the superabsorbent composite. The water absorbency of PAM/ H+-APT and PAM/HDTMABr-APT series superabsorbent composites in distilled water and in 0.9 wt% NaCl solution were measured and are shown in Fig. 4 as a function of APT content in the composites. The results show that the water absorbency for PAM/HDTMABrAPT series are always higher than that for the PAM/ H+-APT series both in distilled water and in 0.9 wt% NaCl solutions in the range of APT content investigated. This is attributed to the fact that the accession of HDTMABr-APT into PAM system results in the improvement of the polymeric network. H+-APT is exchanged by the HDTMABr ion and the long alkyl chains are attached to the surface of APT microparticles like tadpoles, which results in the formation of tiny hydrophobic regions in the polymeric network. The long alkyl chains are curly in the polymeric network when the composite is in a dry state, while they are unfolded owing to the repulsion among the hydrophobic long alkyl chains when the PAM/HDTMABr-APT composite is swollen in water. In the case of PAM/H+-APT, it is only the repulsion among hydrophilic groups (such as COOH and COO) that expands the polymeric

3. Results and discussion 3.1. IR spectra The FTIR spectra of H+-APT, HDTMABr-APT, PAM, PAM/H+-APT and PAM/HDTMABr-APT composites are shown in Figs. 1 and 2, respectively. The absorption bands at 2926 cm1 and 2855 cm1 (Fig. 1(b)) ascribed to masCH and msCH of the hexadecyl of HDTMABr conrm the organication of APT. The hydrolysis of amide is conrmed by the appearance of absorption bands at 1565 cm1 (Fig. 2(a)), 1563 cm1 (Fig. 2(b)) and 1563 cm1 (Fig. 2(c)) attributed toCOO. The appearance of absorption bands (Fig. 2(b) and (c)) at 1679 cm1, 1563 cm1 and 516 cm1 attributed to CONH2, COO and O SiO bends gives direct evidence for the reaction between APT and AM comparing with the spectra of APT (Fig. 1(a) and (b)) and PAM (Fig. 2(a)). The disappearance of SiOH deformation at 989 cm1 (Fig. 2(b) and (c)) comparing with the spectra of H+-APT (Fig. 1(a)) also proves the participation of SiOH in the formation of the composite and this result conforms to our previous study [25].

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Fig. 1. IR spectra of (a) H+-APT and (b) HDTMABr-APT.

Fig. 2. IR spectra of (a) PAM, (b) PAM/H+-APT and (c) PAM/HDTMABr-APT.

network, and then results in the swelling of the composite, while there is also repulsion among hydrophobic groups for the PAM/HDTMABr-APT composite, which also contributes to the swelling of the PAM/ HDTMABr-APT composite and results in a higher water absorbency. Moreover, higher water absorbency of the PAM/HDTMABr-APT composite may also be attributed to the following fact. The hydrogen bond interaction between hydrophilic groups (such as COOH, COO, CONH2 and OH), which prevents the expansion of the polymeric network, is weakened

by the introduction of long alkyl chains. The resulting network is more loosely crosslinked and can expand to a greater extent. Additionally, the long alkyl chains act as obstructers for the reaction between propagating radicals and monomeric double bonds, which means the opportunity for cyclization reaction of MBA increases, and then the network is also less crosslinked and therefore swells more [28]. Furthermore, this gure also indicates that the water absorbency both in distilled water and in 0.9 wt% NaCl solutions increases with increasing a small amount of

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J. Zhang et al. / European Polymer Journal 41 (2005) 24342442

b c

network only acts as crosslinking points and more crosslinking points is generated with increasing the amount of H+-APT. Additionally, the amount of hydrophilic groups in the composite decreases with the increase of H+-APT content (the hydroxy group on H+-APT does not dissociate according to Flory ionic swelling theory [25]), which causes the decrease of osmotic pressure difference between the polymeric network and the external solution, and then the shrinkage of the composite. The results are in conformity with some previous literatures [12,15]. 3.4. Eect of APT on water absorbency of the superabsorbent composites in various saline solutions

10

12

14

2-theta ()

Fig. 3. XRD powder patterns for (a) H+-APT, (b) HDTMABrAPT and (c) PAM/HDTMABr-APT composite doped with 10 wt% HDTMABr-APT.

2800 2450 2100

120

110

Q (g g-1)

b
1750

100

c
1400 1050 700

90

d
80

70 0 5 15 10 APT content (wt%) 20 25

Fig. 4. Eect of APT content in the superabsorbent composites on water absorbencies: (a) PAM/HDTMABr-APT composite in distilled water, (b) PAM/HDTMABr-APT composite in 0.9 wt% NaCl, (c) PAM/H+-APT composite in distilled water and (d) PAM/H+-APT composite in 0.9 wt% NaCl.

Considering the great impact of external saline solutions on the swelling behaviors of superabsorbent polymeric gels and the expanding of their applications especially for hygienic products and horticulture, the interactions of saline solutions and hydrophilic groups on the superabsorbent composites and the swelling behavior of the superabsorbent composites in various salt solutions were investigated in this section. The water absorbencies for PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/HDTMABr-APT composite doped with 10 wt% HDTMABr-APT in NaCl(aq), MgCl2(aq), CaCl2(aq) and FeCl3(aq) are shown in Figs. 58, respectively, as a function of concentration. It can be seen from these gures that the water absorbencies for these superabsorbents in various saline solutions decrease with the increasing concentration of various external saline solutions. This phenomenon is mainly caused by the cations in various salt solutions. The osmotic pressure dierence between the polymeric network and the external saline solution decreases with

Q (g g-1)

1100 1000 900

PAM + PAM/H -APT PAM/HDTMABr-APT

HDTMABr-APT when the content is less than 10 wt%, and then decreases with further increasing HDTMABrAPT content to 25 wt% for the PAM/HDTMABr-APT series. This is because the eect of organo-APT on the improvement of the polymeric network of the composite is not evident with the incorporation of a small amount of it (less than 10 wt%). This means that the maximum water absorbency can be obtained when the composite comprising a suitable amount of organo-APT and the composite doped with 10 wt% HDTMABr-APT possesses the highest water absorbency of 2800 g g1 under our experimental conditions. In the case of PAM/H+APT series, the water absorbency decreases with increasing H+-APT content from 5 wt% to 25 wt%. This result can be attributed to the fact that H+-APT in the

800 700

Q (g g-1)

600 500 400 300 200 100 0 20 40 60 Concentration (mmol L-1) 80 100

Fig. 5. Water absorbencies for PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/HDTMABr-APT composite doped with 10 wt% HDTMABr-APT in NaCl(aq) solutions with various concentration.

J. Zhang et al. / European Polymer Journal 41 (2005) 24342442

200 180 160 140 120 40

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PAM + PAM/H -APT PAM/HDTMABr-APT

35 30 25 20 15 10 5

PAM + PAM/H -APT PAM/HDTMABr-APT

Q (g g-1)

100 80 60 40 20 0 0 20 40 60 Concentration (mmol L-1) 80 100

Q (g g-1)

20

40 60 Concentration (mmol L-1)

80

100

Fig. 6. Water absorbencies for PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/HDTMABr-APT composite doped with 10 wt% HDTMABr-APT in MgCl2(aq) solutions with various concentration.

Fig. 8. Water absorbencies for PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/HDTMABr-APT composite doped with 10 wt% HDTMABr-APT in FeCl3(aq) solutions with various concentration.

160 140 120 100

PAM + PAM/H -APT PAM/HDTMABr-APT

80 60 40 20 0 0 20 40 60 80 100

Concentration (mmol L-1)

Fig. 7. Water absorbencies for PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/HDTMABr-APT composite doped with 10 wt% HDTMABr-APT in CaCl2(aq) solutions with various concentration.

the increase of saline solution concentration according to Florys network theory [25]. The penetration of counterions (Na+, Mg2+, Ca2+ and Fe3+) into the polymeric network makes the screening eect of them on anionic group (COO) more evident, which also decreases the water absorbencies for these superabsorbents [29]. In addition, the complexing ability of carboxylate groups on the superabsorbent network can induce the formation of intramolecular and intermolecular complex with divalent and trivalent cations (such as Mg2+, Ca2+ and Fe3+). As a result, the water absorbencies for these superabsorbents decrease as the increase in concentrations of external saline solutions. Furthermore, the water absorbencies for these three superabsorbents decrease in the order NaCl(aq) > MgCl2(aq) > CaCl2(aq) >

FeCl3(aq). The water absorbency decreases to zero when the superabsorbents were immersed into divalent (Mg2+ and Ca2+) and trivalent cations (Fe3+) of higher concentration, but not for univalent cation (Na+). These results are because of the complexing ability of carboxylate groups on superabsorbent network to cations. The complexing ability of carboxylate group to these four cations are in the order Na+ < Mg2+ < Ca2+ < Fe3+ according to their formation constants with ethylenediamine tetraacetic acid (EDTA, the logarithm of formation constants of EDTA with cations is 0, 8.7, 10.69 and 25.10 for Na+, Mg2+, Ca2+ and Fe3+, respectively). It also can be seen from these gures that the water absorbencies for these superabsorbents are in the order PAM < PAM/H+-APT < PAM/HDTMABr-APT in various external saline solutions of the same concentration. This tendency for PAM/HDTMABr-APT and PAM/H+-APT series in salt solutions is similar to that of in distilled water (comparing Figs. 58 with Fig. 4). This phenomenon may be attributed to the fact that APT is a kind of salt resistant clay and the introduction of APT into the polymeric network results in the generation of a salt resistant superabsorbent composite. Comparing with PAM/H+-APT composite, the higher water absorbency for PAM/HDTMABr-APT composite in various saline solutions may be due to the fact that the long alkyl chains of HDTMABr can interfere the formation of complex between carboxylate groups and cations and weaken the screening eect of cations. To investigate the relationship between water absorbency of the composite and the ionic strength of external saline solutions, the water absorbency of all the three superabsorbents in NaCl solutions of various ionic strengths was investigated and the result was shown in Fig. 9. Hermans had suggested that the relation between

Q (g g-1)

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110 100 90 80 70

J. Zhang et al. / European Polymer Journal 41 (2005) 24342442

3000

PAM + PAM/H -APT PAM/HDTMABr-APT

2500 2000

Q * 10

60 50 40 30 20 10 0 0.0 0.1 0.2 0.3 1/I *10-3 0.4 0.5 0.6

Q (g g-1)

-3

1500 1000 500 0 -20 0 20 40 60 80 100 120 140 160 180 200

5/3

PAM + PAM/H -APT PAM/HDTMABr-APT

Time (min)

Fig. 9. Water absorbency plots for PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/ HDTMABr-APT composite doped with 10 wt% HDTMABrAPT against the ionic strength of NaCl solution.

Fig. 10. Swelling rates in distilled water for PAM, PAM/H+APT composite doped with 10 wt% H+-APT and PAM/ HDTMABr-APT composite doped with 10 wt% HDTMABrAPT. Table 1 Initial swelling rates in distilled water for PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/HDTMABrAPT composite doped with 10 wt% HDTMABr-APT Samples PAM PAM/H+-APT PAM/HDTMABr-APT 198 159 109

swelling ability of superabsorbents and ionic strength of external solution is according to the following equation [30]:
=3 2 Q5 eq A Bi =I

where Qeq is saturated absorbency, i is the charge density on the gel, I is the ionic strength of external solution, A and B are empirical parameters. The saturated water =3 absorbency for a superabsorbent Q5 eq is in inverse proportion to the ionic strength of external solution (I) according to Eq. (2). It can be seen from Fig. 9 that there is an approxi=3 mately linear relationship between Q5 and 1/I all eq through the range of I investigated except that only little discrepancy is observed. This event is due to the fact that the swelling force is interfered by the elastic force of the polymeric chains. 3.5. Eect of APT on swelling rate for the superabsorbent composites Swelling rate for PAM, PAM/H+-APT and PAM/ HDTMABr-APT superabsorbents in distilled water is shown in Fig. 10. It has been reported that the swelling rate of superabsorbent is mainly determined by swelling ability, surface area, particle size and density of the polymer [28]. The curves of swelling rate for PAM and PAM/H+-APT are atter than that for the PAM/HDTMABr-APT composite. This is because the PAM/HDTMABr-APT composite acquires a higher swelling capability and a looser polymeric network, owing to the organication of APT. The initial swelling rates of these three superabsorbents are shown in Table 1. The values in Table 1 indicate that the initial swelling rate is in the order PAM/HDTMABr-APT >

Initial swelling rate (Q/min) 1 min 157 180 13 min 125 147 35 min 65 84

PAM/H+-APT > PAM. Lee et al. reported that the initial swelling rate is primarily due to the penetration of water into the polymeric network through diusion and capillarity [29]. A higher initial swelling rate in distilled water is obtained when APT is introduced to the PAM system. This behavior is because the hydroxy group on the surface of APT increases the anity of the polymeric network to water molecules. Another reason for the PAM/HDTMABr-APT composite acquiring the highest initial swelling rate is that the network is relatively loose and the capillarity is more evident, which accelerate the penetration of water molecules into the polymeric network. 3.6. Eect of APT on reswelling capability of the composites Fig. 11 shows saturated water absorbencies for PAM, PAM/H+-APT and PAM/HDTMABr-APT superabsorbents in distilled water as a function of reswelling times. The curves in Fig. 11 show that saturated water absorbencies for all the three superabsorbents decrease with the increase of reswelling times, and the resulting dry samples after several times of reswelling still retain a high degree of water absorbing capability. These

J. Zhang et al. / European Polymer Journal 41 (2005) 24342442

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4. Conclusions
2800 2400 2000

PAM + PAM/H -APT PAM/HDTMABr-APT

1600 1200 800 400 0 1 2 3 4 5

Swelling-deswelling-swelling times

Fig. 11. Reswelling ability of PAM, PAM/H+-APT composite doped with 10 wt% H+-APT and PAM/HDTMABr-APT composite doped with 10 wt% HDTMABr-APT in distilled water.

The eects of acidied attapulgite and organoattapulgite on water absorbency for the superabsorbent composite in distilled water and in various saline solutions were investigated. The water absorbency for the superabsorbent composite is greatly enhanced by introducing a small amount of organo-APT to the polymeric system. The impact of external saline solutions on the water absorbency for the composite is correlated with the valence of cations and the complexing ability of hydrophilic groups with them. There is an approximately linear relationship between Q5/3 and 1/I for the superabsorbents investigated in aqueous NaCl solution and is accordant with Hermans equation. The examination of swelling rate and reswelling ability of the superabsorbent composites reveals that the composite incorporated with organo-attapulgite exhibits a higher swelling rate and a better reswelling ability comparing with that of doped with acidied attapulgite.

superabsorbent composites may be proved useful in recyclable superabsorbent materials. The PAM superabsorbent acquires the highest water absorbency comparing with PAM/H+-APT and PAM/HDTMABr-APT composites after 5 times of reswelling, although the saturated water absorbency of it is lower than the composites. This behavior means that the water absorbencies for the composites decrease apparently with increasing reswelling times, and reswelling has a more evident eect on the water absorbency of the composites doped with APT. Saturated absorbencies for the PAM/H+-APT and PAM/HDTMABr-APT composites decrease from 2146 g g1 to 610 g g1 and from 2803 g g1 to 733 g g1, respectively, after ve times of reswelling, while it is from 2161 g g1 to 923 g g1 for the PAM superabsorbent and 42.7% of its initial saturated absorbency is retained. This eect can be explained by the incorporation of H+-APT or HDTMABr-APT into the PAM polymeric system. It has been explained above that the network of the superabsorbent composite is less crosslinked owing to the introduction of H+-APT or HDTMABr-APT to the system. According to Florys network theory [25], saturated absorbency of superabsorbent increases with the decrease of the crosslinking density, but on the other hand the intensity of swollen gels is weakened, which means that it has less capability to reswell. In addition, it also can be seen from Fig. 11 that the water absorbency of the PAM/HDTMABr-APT composite is always higher than that of the PAM/ H+-APT composite. This indicated that the organication of APT does not decrease the reswelling capability of the superabsorbent composite as it enhances the saturated water absorbency for the composite.

Q (g g )

-1

Acknowledgements This work was nancially supported with the Western Action Project of CAS (No. KGCXZ-SW-502) and 863 major project of the Ministry of Science and Technology, PR China (No. 2002AA6Z0310701).

References
[1] US Department of Agriculture. US Patent 1961; 3,981,100. [2] Fanta GF, Burr RC, Doane WM, Russell CR. J Appl Polym Sci 1979;24:1384. [3] Fanta GF, Burr RC, Doane WM. J Appl Polym Sci 1979;24:2015. [4] Nagasuna K, Suminaga N, Kimura K, Shimonura T. Jpn Patent 1989; 126,234. [5] Fujio A, Komae T, Yutaka Y. Jpn Patent 1989; 210,463. [6] Sakiyama T, Chu CH, Fujii T, Yano T. J Appl Polym Sci 1993;50:2021. [7] Buchholz FL, Graham T. Modern superabsorbent polymer technology. New York: Wiley-VCH; 1998. p. 1 and 152. [8] Buchholz FL, Peppas NA, editors. Superabsorbent polymers science and technology. ACS Symposium Series, vol. 573, 1994. p. 121. [9] Sun X, Zhang G, Shi G, Tang B, Wu Z. J Appl Polym Sci 2002;86:3712. [10] Ende M, Hariharan D, Pappas NA. React Polym 1995;25: 127. [11] Dorkoosh FA, Brusee J, Verhoef JC, Borchard G, Tehrani MR, Junginger HE. Polymer 2000;41:8213. [12] Li A, Wang AQ, Chen JM. J Appl Polym Sci 2004;92:1596. [13] Dzionmwa GPT, Wood CJ, Hill DJT. Polym Adv Technol 1997;8:762. [14] Wu JH, Wei YL, Lin SB. Polymer 2003;44:6513. [15] Lee WF, Yang LG. J Appl Polym Sci 2004;92:3422.

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J. Zhang et al. / European Polymer Journal 41 (2005) 24342442 [24] Omidian H, Hashemi SA, Sammes PG, Meldrum IG. Polymer 1998;39:6697. [25] Flory PJ. Principles of polymer chemistry. Ithaca, NY: Cornell University Press; 1953. p. 580. [26] Ke YC, Stroeve P. Polymer/inorganic nanocomposites. Beijing: Chemical Industrial Press; 2002. p. 38. [27] Murray HH. Appl Clay Sci 2000;17:207. [28] Elliott JE, Macdonald M, Nie J, Bowman CN. Polymer 2004;45:1503. [29] Lee WF, Wu RJ. J Appl Polym Sci 1996;62:1099. [30] Hermans JJ. Flow properties of disperse system. New York: Wiley-Interscience; 1953. p. 61.

[16] Kabiri K, Zohuriaan-Mehr MJ. Macromol Mater Eng 2004;289:653. [17] Lin J, Wu J, Yang Z, Pu M. Macromol Rapid Commun 2001;22:422. [18] Wu J, Lin J, Zhou M, Wei C. Macromol Rapid Commun 2000;21:1032. [19] Gao D, Heimann RB, Lerchner J, Seidel J, Wolf G. J Mater Sci 2001;36:4567. [20] Ray SS, Okamoto M. Prog Polym Sci 2003;28:1539. [21] Neaman A, Singer A. Appl Clay Sci 2004;25:121. [22] Li A, Wang AQ, Chen JM. J Appl Polym Sci 2004;94:1869. [23] Dainton FS, Tordo M. Trans Faraday Soc 1958;53:666.

Bioresource Technology 98 (2007) 327332

Utilization of starch and clay for the preparation of superabsorbent composite

An Li, Junping Zhang, Aiqin Wang
*
Centre for Ecological and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China Received 19 September 2005; received in revised form 27 December 2005; accepted 29 December 2005 Available online 21 February 2006

Abstract Starch and attapulgite were utilized as raw material for synthesizing starch-graft-poly(acrylic acid)/attapulgite superabsorbent composite by graft copolymerization reaction of starch and acrylic acid (AA) in the presence of attapulgite micropowder in aqueous solution. Major factors aecting on water absorbency such as weight ratio of AA to starch, initial monomer concentration, neutralization degree of AA, amount of crosslinker, initiator and attapulgite were investigated. The superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10 wt% exhibit absorption of 1077 g H2O/g sample and 61 g H2O/g sample in distilled water and in 0.9 wt% NaCl solution, respectively. This superabsorbent composite with excellent water absorbency and water retention under load, being biodegradable in nature, economical and environment-friendly, could be especially useful in agricultural and horticultural applications. 2006 Published by Elsevier Ltd.
Keywords: Starch; Attapulgite; Superabsorbent composite; Water absorbency; Water retention

1. Introduction Superabsorbents are three-dimensionally crosslinked hydrophilic polymers capable of swelling and retaining possibly huge volumes of water in swollen state. Since the rst superabsorbent polymer was reported by the US Department of Agriculture (Weaver et al., 1976), superabsorbents have received signicant attention, especially in the past 30 years, because of their considerable applications in many areas such as sanitary goods (Gross, 1990; Buchholz, 1990; Lokhande and Gotmare, 1999), agriculture and horticulture (Mohana Raju and Padmanabha Raju, 2001; Yao et al., 1994; Zhou et al., 1996; Lokhande and Varadara, 1992), waste-water treatment (Davies et al., 2004), medicine for drug delivery system (Colombo, 1993; Dong and Homan, 1991) and so on.

Corresponding author. Tel.: +86 931 4968118; fax: +86 931 8277088. E-mail address: aqwang@lzb.ac.cn (A. Wang).

Superabsorbent polymers are used mainly as absorbents in healthcare and agriculture applications. In such applications, water absorbency and water retention are essential. Although the superabsorbents based on synthetic polymers do have large uid absorbing capacities, those prepared from saponied starch graft copolymers have a greater demand in industry due to their low cost and also because of the large proportion of starch in these gels which render them biodegradable and thus environmental friendly. Recently, the preparation of polymer/clay superabsorbent composite has attracted great attention because of their relative low production cost, high water absorbency and their considerable applications in agriculture and horticulture (Wu et al., 2000; Lin et al., 2001). In our previous study, the preparation of superabsorbent composite based on acrylic monomer and clay have been reported (Li et al., 2004; Li and Wang, 2005). In a continuation of our research in the eld of organicinorganic superabsorbent composite, we have directed our attention towards the preparation of starch-based superabsorbent composite.

0960-8524/$ - see front matter 2006 Published by Elsevier Ltd. doi:10.1016/j.biortech.2005.12.026

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Attapulgite (a kind of clay mineral), as a good substrate for superabsorbent composite materials, is a layered aluminium silicate with reactive groups OH on the surface. In addition, starch and attapulgite are low cost raw materials. So, the chemical blending by means of graft copolymerization reaction of acrylic acid, starch and attapulgite and fabricating a superabsorbent composite can signicantly reduce the production cost and improve the comprehensive water-absorbing properties of the superabsorbent materials. In this paper, we report the synthesis of superabsorbent composites by graft copolymerization reaction of starch and acrylic acid using N,N 0 -methylene-bisacrylamide as a crosslinker and ammonium persulphate as an initiator in the presence of attapulgite micropowder in an aqueous solution. Aspects investigated included the optimum synthesizing conditions. 2. Experimental 2.1. Materials

The procedure of preparation of crosslinked starchgraft-poly(acrylic acid) superabsorbent polymer was similar to that of preparation of superabsorbent composite, except attapulgite was omitted. 2.3. Water absorbency measurement A weighted quantity of the superabsorbent composite was immersed in distilled water or saline solutions at room temperature to reach the swelling equilibrium. Swollen samples were then separated from unabsorbed water by ltered over a 100-mesh screen. The water absorbency (QH2 O ) of superabsorbent composite was determined by weighing the swelled samples, and the QH2 O of the samples was calculated using the following equation: QH2 O m2 m1 =m1 1

where m1 and m2 are the weights of the dry sample and the water-swollen sample, respectively. QH2 O was calculated as grams of water per gram of sample. 2.4. Characterization

Potato starch was obtained from Huaou Starch Co., Ltd., Inner Mongoulia, China. Acrylic acid (AA, chemically pure, Shanghai Wulian Chemical Factory, Shanghai, China) was distilled under reduced pressure before use. Ammonium persulphate, (APS, analytical grade, Xian Chemical Reagent Factory, Xian, China) was recrystallized from water. N,N 0 -methylene-bisacrylamide, (MBA, chemically pure, Shanghai Chemical Reagent Corporation, Shanghai, China) was used as purchased. Attapulgite micropowder, (Linze Colloidal Co., Gansu, China), milled and passed through 320-mesh screen, followed by a treatment with 37% hydrochloric acid for 48 h and washed with distilled water until pH 7 was reached, and then dried at 105 C for 8 h prior to use. All solutions were prepared with distilled water. 2.2. Preparation of superabsorbent composites and crosslinked starch-graft-poly(acrylic acid) polymer A series of the samples with dierent amounts of attapulgite, crosslinker, initiator, starch and acrylic acid with dierent degrees of neutralization were prepared by the following procedure: A weight quantity of starch and distilled water were put in a 250-mL four-necked ask equipped with a stirrer, a condenser, a thermometer, and a nitrogen line. The slurry was heated to 95 C for 30 min under nitrogen atmosphere. The initiator APS was then added when the temperature reached 6065 C. After 15 min, the partially neutralized AA, crosslinker (MBA) and attapulgite mixture solution was added. The water bath was heated slowly to 70 C and kept for 3 h. Then the resulting product was washed several times with distilled water and ethanol and then dried at 70 C to a constant weight. The dried product was milled and screened. All samples used had a particle size in the range of 4080 mesh.

The IR spectra of the superabsorbent composite were recorded on a FTIR (Thermo Nicolet, NEXUS, TM) using KBr pellets. Thermal stability studies of dry samples were performed on a PerkinElmer TGA-7 thermogravimetric analyzer (PerkinElmer Cetus Instruments, Norwalk, CT), with a temperature range of 25800 C at a heating rate of 10 C/min using a dry nitrogen purge at a ow rate of 50 mL/min. 3. Results and discussions 3.1. IR spectra By comparison with the infrared spectra of attapulgite and starch-graft-poly(acrylic acid)/attapulgite superabsorbent composite (20% attapulgite content), the absorption peaks at 3621 and 3549 cm1 attributed to the OH groups on attapulgite disappeared after reaction, showing that the graft copolymerization between OH groups on attapulgite and acrylic acid monomers took place during the reaction (Li et al., 2004; Li and Wang, 2005). Also, by comparison with the infrared spectra of starch and superabsorbent composite, the absorption peak at 574 attributed to the OH groups on starch became smaller after reaction, which indicated that the OH groups on starch changed during the reaction. According to Wu et al. (2000), this could be due to the fact that the circle of starch was opened and formed CHO and COH groups under the initiator and the graft polymerization between COH groups on starch and the acrylic acid monomers took place. The IR analysis results indicated that the graft copolymerization of acrylic acid monomer on both attapulgite and starch took place during polymerization process and the resulting product was a composite

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based on PAA incorporating with starch and attapulgite (results not shown). 3.2. Thermal analysis The thermogravimetic analysis (TGA) of crosslinked starch-graft-poly(acrylic acid) polymer and starch-g-poly(acrylic acid) superabsorbent composite (20% attapulgite content) were also carried out. Both crosslinked starchgraft-poly(acrylic acid) polymer and starch-g-poly(acrylic acid) superabsorbent composite showed a very small weight loss below 100 C, implying a loss of moisture. Starch-graft-poly(acrylic acid) polymer and starch-g-poly(acrylic acid) superabsorbent composite had signicant weight loss of 12.3% and 19.7% at 274 and 336 C, respectively. The major weight loss of starch-graft-poly(acrylic acid) polymer started at 391 C (66.7%), whereas for starch-g-poly(acrylic acid) superabsorbent composite the major weight loss started at 450 C (59.0%). Therefore, starch-graft-poly(acrylic acid) polymer and starch-g-poly(acrylic acid) superabsorbent composite had a decomposition temperature of 391 and 450 C, respectively. The results indicated that the introduction of attapulgite to polymer network resulted in an increase in thermal stability (results not shown). 3.3. Eect of weight ratio of AA to starch Table 1 showed that the water absorbency of superabsorbent composite increased with increasing content of AA. The maximum water absorbency was reached when the superabsorbent composite was synthesized with a weight ratio of AA to starch of 5:1. It could be due to the fact that both grafting and the molecular weight of the grafted PAA chain increased with an increase in AA content (Reyes et al., 1968). With further increasing AA content, the water absorbency decreased. This could be attributed to an increase in homopolymer percentages of PAA, which in turn resulted in an increase in soluble materials at xed crosslinking density (Reyes et al., 1969). 3.4. Eect of initiator content The eect of initiator content on water absorbency is shown in Table 2. Increase in the content of APS resulted
Table 1 Eect of weight ratio of AA to starch in the feed on the water absorbency of the superabsorbent compositea Weight ratio of AA to starch 3:1 4:1 5:1 6:1
a

increase in water absorbency of the superabsorbent composite, which reached a maximum of 1077 g/g at a APS content of 0.3%. Further increase in APS resulted in the decline of water absorbency of superabsorbent composite. This could be due to the fact that the initiator were mostly utilized in producing a large number of free-radical sites on the starch backbone at which the monomers could be grafted when the initiator content was low (Athawale and Lele, 2000). Therefore, the grafting yield, and, in turn, the absorbency of the graft polymer increased with increase in APS content. However, above a critical content of 0.3%, the excess of APS was utilized in the homopolymerization of monomers, which resulted in the decrease of the water absorbency. 3.5. Eect of crosslinker content The eect of crosslinker content on water absorbency is shown in Table 2. As can be seen, the water absorbency decreased with the increase of crosslinker content from 0.08% to 0.2%. Clearly, higher crosslinker content resulted in the generation of more crosslink points, which, in turn, caused the formation of an additional network and decreased the available free volume within the superabsorbent composite. When the crosslinker content was lower than 0.08%, the absorbency of superabsorbent composite decreased because of an increase of soluble material. This tendency was similar to poly(acrylic acid)/attapulgite superabsorbent composite prepared by Li et al. (2004) and other superabsorbent hydrogels prepared by Chen and Zhao (1999, 2000). 3.6. Eect of initial monomer concentration The eect of initial AA concentration (CA, wt%) on water absorbency is also shown in Table 2. It was dicult to obtain a composite gel in the preparation when CA was less than 13.4% and water absorbency was hard to measure exactly because of the excessive water soluble material. The water absorbency in distilled water increased from 624 to 1077 g/g as CA increased from 13.4% to 18.4% and decreased with further increases in CA. Baker et al. (1992) reported that the eective crosslinking density was probably less than the nominal crosslinking density at a low total monomer concentration in the preparation of cationic acrylamide-based hydrogel. It was responsible for the decrease in the water absorbency with further increase in CA. The result for starch-g-poly(acrylic acid)/attapulgite superabsorbent composite were in conformity with the resulting cationic acrylamide-based hydrogel and similar observations have been reported by others (Chen and Zhao, 2000; Lee and Yeh, 1997). 3.7. Eect of neutralization degree of AA As shown in Table 2, the water absorbency increased with the increase of neutralization degree from 10% to 40% and

Water absorbency (g/g) 278 626 1077 671

Reaction conditions: reaction temperature, 70 C; 40% neutralization degree of AA; initial AA concentration (CA), 18.4 wt%; weight ratio of initiator, crosslinker and attapulgite in the feed is 0.3 wt%, 0.08 wt% and 10 wt%, respectively.

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Table 2 Eect of initiator content, crosslinker content, initial concentration of AA and neutralization of AA on the water absorbencies of the superabsorbent compositesa Initiatora Content (wt%) 0.1 0.3 0.5 0.8 1.0 Qeq 47 1077 822 600 580 Crosslinkerb Content (wt%) 0.08 0.09 0.10 0.15 0.20 Qeq 1077 880 657 586 507 AAc Concentration (wt%) 13.4 15.5 18.4 22.5 29.0 Qeq 624 805 1077 847 572 AAd Neutralization degree (%) 20 30 40 50 60 Qeq 479 813 1077 974 659

Qeq: equilibrium water absorbency, (g/g). a Reaction conditions: reaction temperature, 70 C; 40% neutralization degree of AA; weight ratio of AA to starch, 5:1; CA, 18.4 wt%; weight ratio of crosslinker and attapulgite in the feed is 0.08 wt% and 10 wt%, respectively. b Reaction conditions: reaction temperature, 70 C; 40% neutralization degree of AA; weight ratio of AA to starch, 5:1; CA, 18.4 wt%; weight ratio of initiator and attapulgite in the feed is 0.3 wt% and 10 wt%, respectively. c Reaction conditions: reaction temperature, 70 C; 40% neutralization degree of AA; weight ratio of AA to starch, 5:1; weight ratio of initiator, crosslinker and attapulgite in the feed is 0.3 wt%, 0.08 wt% and 10 wt%, respectively. d Reaction conditions: reaction temperature, 70 C; weight ratio of AA to starch, 5:1; CA, 18.4 wt%; weight ratio of initiator, crosslinker and attapulgite in the feed is 0.3 wt%, 0.08 wt% and 10 wt%, respectively.

decreased with further increase in the neutralization degree of AA. When AA was neutralized with sodium hydroxide, the negatively charged carboxyl groups attached to the polymer chains set up an electrostatic repulsion, which tended to expand the network. In a certain range of neutralization degree, the electrostatic repulsion increased with the increase of neutralization degree, resulting in the increase of water absorbency. When the neutralization degree of AA was above the optimum values, the swelling capacity of superabsorbent composite decreased. This behavior could be ascribed to an increase in chain stiness and to counterion condensation on the polyion (Ende et al., 1995). Similar observation was reported by Buchanan et al. (1986) on investigating the water retention of polyacrylate networks as a function of the degree of neutralization. They found that the chain could expand to such an extent that the distance between neighboring charges became too high for optimum cooperation eects between the charges. 3.8. Eect of attapulgite Table 3 shows the eect of attapulgite content on the water absorbency. The water absorbency decreased with
Table 3 Eect of amount of attapulgite on the water absorbencies of the superabsorbent compositesa Sample no. Attapulgite percentage (wt%) 0 10 20 30 40 QH2 O (g/g) Distilled water St-PAA/At0 St-PAA/At1 St-PAA/At2 St-PAA/At3 St-PAA/At4
a

the increase of attapulgite content. Chen and Zhao (1999, 2004) reported that the inorganic clay mineral particle in network acted as an additional network point. The crosslinking density of superabsorbent composite increased with the increase of attapulgite content, which resulted in a decrease in water absorbency. Table 3 also showed that the superabsorbent composites had high water-absorbing capacity in both distilled water and 0.9% NaCl solution as compared with crosslinked starch-g-poly(acrylic acid) polymer, especially when the superabsorbent composite contained low percentage of attapulgite. 3.9. Eect of saline solutions Fig. 1 shows the eect of the concentration of saline solutions (NaCl(aq); CaCl2(aq) and FeCl3(aq)) on water absorbency of superabsorbent composite (St-PAA/At1). The water absorbency decreased with the increase of the concentration of all three saline solutions. According Hermans

180 160 140 NaCl CaCl2 FeCl3

Water absorbency (g/g)

120 100 80 60 40 20 0 0.0 0.2 0.4 0.6 0.8 1.0

0.9 wt% NaCl 39 61 53 50 43

369 1077 775 554 543

Reaction conditions: reaction temperature, 70 C; 40% neutralization degree of AA; weight ratio of AA to starch, 5:1; CA, 18.4 wt%; weight ratio of initiator and crosslinker in the feed is 0.3 wt% and 0.08 wt%, respectively.

Concentration of salt solution (wt %)

Fig. 1. Water absorbency of St-PAA/At1 in NaCl, CaCl2, and FeCl3 aqueous solutions with various salt concentration.

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(1953), the water absorbency of superabsorbent decreased with increase of ionic strength of external solution. This decrease in water absorbency with increasing ionic strength could be attributed to the decrease in the osmotic pressure dierence between the superabsorbent composite and the external saline solutions. Fig. 1 also showed that for a given concentration of saline solution, the water absorbency in NaCl solution was far higher than that of in CaCl2 and FeCl3 solutions. This dramatic decrease of water absorbency in multivalent cationic solutions could be due to the complexing ability of the carboxylate groups inducing the formation of intramolecular and intermolecular complexes, which resulted in an increase in the crosslinking density of network (Castal et al., 1990). 3.10. Swelling rate Fig. 2 indicated that the swelling rate of superabsorbent composite was high in 010 min and the water absorbency of superabsorbent composite reached 809 g/g within 10 min. After 10 min, the swelling rate became low and the maximum swelling capacity of superabsorbent composite was reached within 90 min. 3.11. Water retention test Water retention of the swollen superabsorbent composites was determined by a heating oven test at dierent temperatures. Fig. 3 shows the water retention capacity of swollen superabsorbent composite (St-PAA/At1, 25 g) as a function of time at 60 and 100 C. The swollen sample had a decreasing tendency of the water retention with prolonging the time. About 0.3% of distilled water could be held at 60 C after 5 h of water retention test. In the case of 100 C water retention test, the water loss of St-PAA/ At1 almost reached 99.9% after 2 h. Water retention of the swollen superabsorbent composite (St-PAA/At1) was also determined by centrifuging it at 4000 rpm. The result showed that the starch-g-poly(acrylic acid)/attapulgite
1200

100

80

60 C 100 C

Water retertion (%)

60

40

20

Time (h)
Fig. 3. Water retention of swollen samples (St-PAA/At1, 25 g) as a function of time at 60 and 100 C.

superabsorbent composite had a good water retention ability and could keep more than 90% of the distilled water after centrifugation it at 4000 rpm for 10 min. 4. Conclusion A novel starch-graft-poly(acrylic acid)/attapulgite superabsorbent composite was synthesized by graft copolymerization reaction of starch and AA in the presence of attapulgite powder in aqueous solution. The optimum synthesizing conditions were as follows: weight ratio of AA to starch, 5:1; initiator content, 0.3%; crosslinker content, 0.08%; initial AA concentration, 18.4%; AA content: 74.68%; starch content, 14.94%; attapulgite content, 10%. The superabsorbent composite synthesized under optimal synthesis conditions exhibited absorption of 1077 and 61 g H2O/g sample in distilled water and in 0.9% NaCl solution, respectively. This new approach showed promising in utilizing natural resource such as starch and attapulgite in the production of superabsorbent material, which could signicantly reduce the production cost and make the technique quite environmental friendly. Also, this novel superabsorbent composite with excellent water absorbency and water retention under load could be especially useful in agricultural and horticultural applications. Acknowledgements This work was nancially supported by the Western Action Project of CAS (No. KGCXZ-SW-502) and the 863 major project of the Ministry of Science and Technology, PR China (No. 2005AA2Z4030). References

1000

Water absorbency (g/g)

800

600

400

200 0 20 40 60 80 100 120

Time (min)
Fig. 2. Variation of the water absorbency with time for St-PAA/At1.

Athawale, V.D., Lele, V., 2000. Factors inuencing absorbent properties of saponied starch-g-(acrylic acid-co-acrylamide). Journal of Applied Polymer Science 77, 24802485.

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