ELSEVIER

BIORfSOURCf TfGlllO1O~Y
Bioresource Technology 68 (1999) 283-286

Utilization of textile loomwaste as a highly absorbent polymer through graft co-polymerization

H.T. L,okhande*, UwisronTechnology of Flbrrs of V.D. Gotmare
and Tafile Prouwing, Univwsity Department of Chemical Technology (Autonomous), Universily qf Bombay, Matunga, Bombay 400 019, India

Received 7 May 1998; revised 30 July 199X: accepted 3 August 1998

Abstract
Loom waste from cotton textile mills, containing starch (- 30%) and cotton cellulose ( - 70%) was utilized as a starting raw material for synthesizing a product called Loomwaste-g-poly(AN) using a free radical initiation technique. Major factors of polymerization reaction affecting polymerization of acrylonitrile (AN), KMnO, , nitric acid, reaction time and temperature were studied. The product was saponified by boiling it in aqueous NaOH to obtain hydrolysed Loomwaste-g-poly(AN), which is an excellent water absorbent. Saline solution (0.9% NaCI) absorbency was also studied in order to utilize the product in marine fields. The results indicated that this new approach showed promise in utilizing such waste in the production of useful products, which are eco-friendly, biodegradable and could also minimize the disposal problems of the textile industly. 8 1998 Elsevier Science Ltd. All rights reserved.
Keywords: Loomwaste; Acrylonitrile;

Grafting; Superabsorbent;

Infrared; Saline solution

1. Introduction Graft co-polymerization considerable has evoked

effective products, means of onto interest, synthesizing starch as a it and series

cellulose
an new of

provides

such as superabsorbents, with valuable properties. Most of the superabsorbents are derived from depleting expensive petroleum products. Buchholz (lYY4) has reported the preparation of a superabsorbent polymer by free radical-initiated polymerization of acrylic acid and its salts with crosslinkers. Stannet et al. (1985) have reported grafting of starch and cellulose to impart water absorbency and the usefulness of the product in personal care and medical applications. A practical process for the preparation of a super-slurper with a large capacity to absorb water was also reported by Weaver et al. (1977). Caste1 et al. (1YYO) have studied the water and saline absorbency of graft-polymerized starch. Zdhran et al. (1980) used a radiation technique to graft cellulosic fibres, in order to impart high water absorbency.
*Corresponding author. E-mail: textile~udct.ernet.in. tOther publications of H. T. Lokhande can also be found under the name of H. T. Dee.

Lokhande and Vardharajan (1992) and Lokhande et al. (1992) synthesized a guargum-based superabsorbent and successfully used it as a soil additive. Lokhande and Vardharajan, 1993 also studied the production of non-wood-based cellulosic superabsorbents and their water retention capacities. Recently Lokhande and Gotmare (1997) have synthesized starch-based superabsorbents using a redox system (KMnO, as an initiator) and studied their water absorbencies. In another study, they used cotton yarn in the grey state to synthesize Cell-g-Poly(AN), which exhibits high water absorbency on saponification (Lokhande and Gotmare, 1998). The literature shows that raw materials containing either starch or cellulose can be good sources for the synthesis of superabsobents, which could result in wide applications. In the present work, an attempt was made to utilize loomwaste from cotton textile mills, which contains starch with cotton cellulose in the form of small pieces of fibres. It is available at throw-away prices as a starting material for synthesizing a superabsorbcnt using a KMnOJ-HN03 redox system and acrylonitrile (AN) as a monomer. Water and saline absorbencies of these materials show probable uses in various articles such as baby diapers, sanitary napkins, soil additives, etc.

0960-8524/99/S ~ see front matter 0 1998 Elsevier Science Ltd. All rights reserved PII: SO960-8524(98)00148-5

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H. 7: Lukhunde, VD. Go~murelBioresourcr Echnolo~ 68 (1999) 283-286

2. Methods Loomwastc from cotton tcxtilc mills that contained starch (- 30%) and cotton (- 70%) was used for grafting. 2. I. Treatment of loomwaste with potassium perrnanganate (initiator} The loomwaste (2 g) was impregnated in an aqueous solution that contained a specific concentration of KMnO, solution (0.01-0.06 N) and 0.2% non-ionic wetting agent. The treatment was carried out at 55C for a period of 30 min at a material to liquor ratio of 1:lOO with continuous shaking to avoid heterogeneity of MnOz deposition on the material. After this treatment, it was washed with distilled water and squeezed between two filter papers before being introduced into the polymerization solution. 2.2. Graft co-polymerization The permanganate-treated sample was put into a reaction fask that contained a specific concentration of nitric acid (0.025-0.25 M) and acrylonitrile monomer (0.4-8% w/v). A material to liquor ratio of 1:lOO was used. The flask content was kept in a thermostatic water bath at different temperatures (30-80C) and for different reaction times (lo-70 min). At the end of reaction, the samples were washed witit water at room temperature and dried at 105C and cooled over PLOZ. The homopolymer was extracted with dimethyl formamide for 24 h at 35C. The graft add-on was obtained through the estimation of nitrogen by a Kjeldahl method (Vogel, lY71). 2.3. Quantitative loomwaste determination af MnO, deposited on

pH 9 was reached mesh size.

and then dried

and ground

to a 20

2.5. Infrared (IR) confirmation Grafting on Loomwaste-g-Poly(AN) was confirmed by IR analysis. The IR spectrum was recorded in a KBr phase by using a JASCO FT/IR-5300 Model spectrophotometer employing the KBr pallets technique of O Connor et al. (1957). 2.6. Water and saline solution absorbency (filtration method) The method used to determine water and saline solution absorbency has been described in a previous paper (Lokhande and Gotmare, 1998), and expressed as g of HzO/g sample or g saline solution/g sample.

3. Results and discussion 3.1. Analysis of loomwaste of cotton textile mills The loomwaste mass consisted of starch ( - 30%) and cotton fibrous mass ( - 70%), with a micronaire value of 5.35. The Whiteness Index (WI) value (Hunter whiteness) was 35.336 and a considerable improvement in WI to 50.323 was produce by grafting. Thus the eco-damaging scouring and bleaching processes could be totally avoided 3.2. Effect of KMn04 concentration Mn02 deposited on the amount of

The method used to determine the amount of MnOZ deposited on to loomwaste was similar to a method described in a previous paper (Lokhande and Gotmare, 1998) and the results were expressed as mcq/lOO g of sample. 2.4. Saponification Saponification of Loomwaste-g-poly(AN) was carried out as per the method of Lepoture et al. (1973). Grafted loomwaste ( - 2 g) was introduced into 100 ml boiling NaOH solution (3%) and stirred with a magnetic stirrer. Graft co-polymer was formed rapidly in the form of a slurry and had a typical red-orange colour that then slowly faded to light yellow as the reaction neared completion. It was filtered, while hot, through a Buchner funnel and washed with water until

Loomwaste samples treated with KMn04 were monitored for MnOZ deposition. Mn02 deposition increased with increasing KMnO, concentration up to 0.05 N. Above this concentration, when deposition was 24.32 meq/lOO g waste, no marked increase in the MnOz deposition was observed. MnOe deposition was high. This (high deposition) may possibly be because of the fact that starch, with its disordered nature, causes high deposition of MnO,. 3.3. Effect of KMn04 concentration graft-add-on on the percentage

The results describing the effect of KMn04 concentration on the percent graft add-on, were analysed. The graft add-on increased significantly by increasing the KMn04 concentration up to 0.05 N. Above this concentration, the graft add-on almost levelled off. The enhancement in grafting increased as a result of the amount of MnO, absorbed. This may have been caused by the creation of cellulosic macroradicals that are

H.?: Lokhande,

VD. GotmarelBioresource Technology 68 (1999) 283-286

285

capable of initiating the grafting reaction. On the other hand, the levelling off of grafting beyond a certain KMnO, concentration could have been associated with the following facts: Lower rate of monomer diffusion from the aqueous phase to the substrate phase by virtue of excess deposits of Mn02 colloidal particles. Higher production of inhibiting oxygen at higher MnOz concentration because of a side reaction Mn02+2Hf+Mn(II) +HzO+O (1)

effect of high tcmpcraturc associated with:

on grafting

could have been

of the redox system, giving 1. better decomposition rise to the availability of more free radicals, 2. greater swellability of the substrate, 3. incrcascd mobility of the monomer molecules, 4. higher diffusion from the aqueous phase on to the substrate phase, and of the graft 5. higher rate of initiation and propagation chain.

particularly via Faster rate of termination, bimolecular collision between two chain radicals facilitated by the abundance of primary free radical species.

3.7. Effect of reaction time The relationship between reaction time and the graft add-on was examined from 10 to 70 min. It was evident that the graft add-on increased with increase in time. This could be attributed to the depletion of both monomer and initiator molcculcs as the polymerization reaction proceeded. 3.8. The optimal conditions of grafting About 40% graft add-on was obtained by maintaining the following reaction conditions: KMn04 = 0.05 N, HN03 = 0.2 M, Acrylonitrile = 6.4% w/v, M:L.R = l:lOO, temperature = 7OC, time = 60 min. 3.9. Water absorbency and saline solution absorbency Absorbency test with distilled water and saline solution (0.9% NaCl) was carried out for selected samples. The results indicated that the absorbency of about 148 g H,O/g and 63 g saline solution/g of dry sample was obtained for the maximum graft add-on (41.80%) of Poly(AN)-Loomwaste-g-Co-polymer. This observation is in agreement with the results reported by Chen et al. (1985). They showed that the viscosity of the dispersion decreased with an increase in the valency of counter ions and, therefore. the absorbent polyclcctrolytic polymer was unable to hold as much saline solution as pure water. It was observed that the absorbency value for saline solution was only 45-50% of that of the water absorbency value at a given level of graft add-on. 3.10. Infrared spectra

3.4. Effect of concentration

of HNOY

The effect of concentration of nitric acid on percentage graft add-on was examined. It was found that the percentage graft add-on increased with increasing concentration of acid, attaining a maximum at 0.2 M and then falling at further higher concentrations. This could be attributed to the following: The coagulation of colloidal homopolymer in solution and within the substrate during grafting reaction, increases at lower pH. This, in turn, retards diffusion of both monomer and initiator to the substrate. The side reaction, given in scheme (l), increases at a higher acid concentration. Thus, besides consuming some MnOz (required for production of initiating species), this also leads to the constant production of inhibiting oxygen.

3.5. Effect of monomer concentration The acrylonitrile concentrations used ranged from 0.4 to X.0% w/v. As the concentration of acrylonitrile increased, the percentage graft add-on also increased because of greater availability of monomer molcculcs around the cellulose macroradicals. 3.6. Effect qf reaction temperature The effect of change in temperature (30-80C) on percent graft add-on indicated that the percentage graft add-on increased because of raising the polymerization temperature from 30 to 70C. This favourable

The IR spectra of grafted as well as ungrafted loomwaste were recorded. Based on general consideration for assignment of variable absorption bands of starch and cellulose, it was observed that the spectrum of grafted loomwaste showed a characteristic C =N

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H.T Lokhande, VD. GotmareiBioresourceTechnology68 (1999) 283-286

absorption band at 2243 cm- . ence of grafting.

This showed

the exist-

4. Conclusion The new approach adopted in utilizing cotton textile mills loomwaste for the preparation of a superabsorbent graft co-polymer was quite promising. The resultant product showed an exccllcnt water and saline solution absorbencies. The above properties happen to be some of the essential characteristics of a superabsorbent in a variety of commercial applications. The product could serve as an effective substitute for similar products derived from scarce petroleum-based raw materials. Since the raw material (loomwaste) is available for almost no cost and since it contains biodegradable starch and cotton cellulose, the utilization of such a waste material makes the technique quite economical and environment-friendly.

References
Buchholz, F.L., 1994. Keeping dry with superabsorbent polymers. CHEMTECH 24 (9), 3X-43. Chen, CC., Vassallo, J.C., Chatterjee, P.K. 1985. Synthetic and natural polymers, In: Chatterjee, P.K. (Ed.). Absorbency. Elsevier Science Publishers, The Netherlands. pp. 197-215. Castel, D., Richard, A., Audebert, R., 1990. Swelling of anionic and cationic starch-based superabsorbents in water and saline solution. Journal of Applied Polymer Science 39, 11-29.

Lepoture, P., Hui, S.H., Robertson, A.A., 1973. The water absorbency of hydrolyzed polyacrylonitrile-grafted cellulose fibers. Journal of Applied Polymer Science 17, 3143-3156. Lokhande, H.T.. Vardharajan, P.V., Iyer. V., 1992. Water superabsorbent polymer through gamma radiation-induced graft copolymerisation of acrylonitrile. Journal of Applied Polymer Science 45. 2031-2036. Lokhande, H.T., Vardharajan, P.V.. 1992. A new guargum based superabsorbent polymer synthesised using gamma radiation as a soil additive. Bioresourcc Technology 42, 119-122. Lokhande, H.T., Vardharajan, P.V., 1993. A new approach in the production of non-wood based cellulosic superabsorbents through the PAN grafting method. Bioresource Technology 45, 161-165. Lokhande, H.T., Gotmare, V.D., 1997. Superabsorbent based on starch and cellulosic polymers. Paper presented at the XIIth Carbohydrate Conference, Lucknow, India, 20-21 November. (Book of papers), Lucknow University (in press). Lokhande, ILT., Gotmare, V.D., 1998. Acrylonitrite monomer grafting on grey cotton to impart high water absorbenq Journal of Applied Polymer Science (in press). O Connor. R.T., Dupre, E.F., MacCall, E.R., 1957. Infrared spectrophotometric procedure for analysis of cellulose and modified cellulose. Analytical Chemistry 29, 998-1005. Stannet, V.T., Fanta, G.F., Deane, W.M., 1985. Polymer grafted cellulose and starch. In: Chatterjee, P.K. (Ed.), Absorbency. Elsevier Science Publishers, The Netherlands, pp. 257-277. Vogel, A.I., 1971. A Text Book of Quantitative Inorganic Analysis. Longmann, London, pp. 256-257. Weaver, M.O., Montgomery. R.R., Miller, L.D., Sohns, V.E., Fanta, G.F., Deane, W.M.. 1977. A practical process for the preparation of super slurper: a starch based polymer with a large capacity to absorb water. Staerke 29 (12), 413-422. Zahran, A.H., Williams, J.L., Stannet, V.T., 1980. Radiation grafting of acrylic and methacrylic acid to cellulose fibres to impart high water absorbency. Journal of Applied Polymer Science 25, 535-542.