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Chinese Chemical Letters 19 (2008) 435437 www.elsevier.com/locate/cclet

Synthesis and study of MPNS/SMA nano-composite tanning agent

Hui Pan *, Mei Qi, Zhi Jun Zhang
Laboratory of Special Functional Material, Henan University, Kaifeng 475004, PR China Received 22 October 2007

Abstract The radical polymerization of maleic anhydride (MA), styrene (ST) with the vinyl groups introduced onto the surface of the nano-sized silica via solution polymerization method was developed. The methacryloxypropyl nano-sized silica (MPNS) was used as macromonomer and polymerized with maleic anhydride and styrene by initiating with BPO in toluene. The structure and properties of MPNS/SMA nano-composite were characterized by FT-IR spectra and TEM. Meanwhile, it was applied as tanning agent compared with the traditional styrenemaleic anhydride copolymer in leather. It was found that the applied leather had better quality characteristics with the addition of the nano-sized silica. # 2008 Hui Pan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Nano-composite; Tanning agent; Polymerization; Leather

The styrenemaleic anhydride copolymer tanning agents have been studied a great deal by technologists and chemists all over the world since the 1970s.The copolymers have been utilized for lling of the tanning and retanning in the manufacture of leather. It has been found that they have good quality characteristics such as fullness, softness and grain effects [1]. However, there are few literatures on polymeric nano-composites composed of styrene and maleic anhydride for making leather in recent years. As is well known, the nano-composites derived from nano-sized inorganic particles and organic compounds are promising new functional materials exhibiting specic properties [2,3], such as quantum effects. If the nano-sized silica particles are dispersed equably and adequately into the resinic materials, the capabilities of the resins will be improved comprehensively due to their small granularities and high activities [46]. The intensities, the abrasion and the ageing resistant qualities of the materials can be enhanced evidently. For example, the transparence, intensity, tenacity and ageing resistance of the PST plastic lm will be increased with the addition of nano-sized silica. In this paper, we have synthesized a new nano-composite material MPNS/SMA and explored its application in the tannage of the sides of sheep skin. The application test shows that the nano-composite induces the higher shrinkage temperature and more increased thickness compared with the traditional SMA copolymer after tanning and retanning. So this is a new type polymeric nano-composite tanning agent with a wide prospect [7].

* Corresponding author. E-mail address: panhui@henu.edu.cn (H. Pan). 1001-8417/$ see front matter # 2008 Hui Pan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. doi:10.1016/j.cclet.2008.01.011

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H. Pan et al. / Chinese Chemical Letters 19 (2008) 435437

Fig. 1. FT-IR spectra of (a) MPNS/SMA, (b) MPNS and (c) SMA.

MPNS was synthesized by our laboratory. The prepare procedure of MPNS/SMA was described as follows: MPNS, ST, MA and dried toluene were charged into a four-neck 250 mL ask, and the mixture was dispersed with ultrasonic vibrations for 15 min. Then the mixture was heated to 55 8C and BPO dissolved in toluene was dropped tardily and continuously within 30 min at this temperature. After that, the mixture was heated to 75 8C and stirred for 2 h at this temperature. Then the mixture was stirred at 85 8C for another 3 h. After cooling the precipitate was ltered and dried in vacuum at room temperature. The resulting product was neutralized with 5% sodium hydrate solution. The nal product is a pale yellow viscous solution. The FT-IR spectra of MPNS/SMA nano-composite (Fig. 1a), MPNS (Fig. 1b) and the poly(STMA) (Fig. 1c) are shown in Fig. 1. The bands, 1100 cm1 of SiOC group, 1698 cm1 of C O, 1652 cm1 of C C group in the spectrum of MPNS. The bands of 703 cm1, 758 cm1, 1856 cm1, 1778 cm1 and 1089 cm1of SiOC group in the spectrum of MPNS/SMA were the testimonies of the success of the polymerization of ST, MA and MPNS. In order to study the tanning suitability of MPNS/SMA nano-composite, it has been used both in tanning and retanning. It is advantageous in the level of application compared with the typical tanning agent of SMA copolymer. The results of the trials are shown in Table 1. Table 1 shows that MPNS/SMA nano-composite possesses better tanning and retanning properties than SMA copolymer. The shrinkage temperature of pickled sheep skin can be increased by 17 8C after tanning with MPNS/SMA, which indicates MPNS/SMA combines rmly with collagen. But the temperature increment begins to reduce with the addition of MPNS, the value reaches the maximum when MPNS content is 3% in polymer. The nano-composite gives the highest value of 70% increase in thickness showing the lling capacity and its use as a tanning lling agent. It is also interesting that the increased thickness reduces evidently with the increasing MPNS. This is probably that the more nanoparticles block the pores embedded the surface of leather and permeate the leather not easily, so the tanning effect is reduced obviously with the increasing concent of MPNS. The SEM photographs of pickled sheep skin (a) and the tanned leather by MPNS/SMA nano-composite (b) are shown in Fig. 2. It is observed that the fasciculus of the tanned leather become unwound after the tanning agents
Table 1 Effects of tanning and retanning leather MPNS content in polymer (%) Increase in shrinkage temperature, DTs (8C) Tanning SMA MPNS/SMA-1# MPNS/SMA-2# MPNS/SMA-3# 0 3 5 7 11 17 8 6 Retanning 3 11 7 4 Increased thickness (%) Tanning 40.4 70.0 35.1 6.5 Retanning 27.8 45.7 33.3 2.1

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Fig. 2. SEM images of (a) the pickled sheep skin and (b) the tanned leather.

Fig. 3. SEM images of (a) the chrome tanning leather and (b) the retanning leather.

permeated the fasciculus. This indicates that the product has certain properties of lling and tanning. That is determined that the leather has better characteristics of chubbiness and increased thickness after tanning by MPNS/ SMA nano-composite. As shown in Fig. 3, the fasciculus of MPNS/SMA retanning leather (b) is thinner, curls more greatly and twisted more loosely than the chrome tanning leather (a). Also the bre disperses all the better. This shows that the nanocomposite can penetrate into the collagen bre to reduce the inner friction, then the segment motion becomes more easily. In conclusion, a facile preparation procedure of styrene and maleic anhydride grafted onto the surface of the methacryloxypropyl nano-sized silica via radical polymerization was developed. The applied test showed that the shrinkage temperature and the thickness of the leather tanned by MPNS/SMA were evidently improved compared with SMA. So it is expected to be a new nano-composite tanning agent and used as ller for tanning and retanning leather. Acknowledgment The authors thank the Leather Engineering College of Shaanxi University of Science & Technology for the assistance of the experiments. References
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