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Composites: Part A 42 (2011) 471477

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Immobilization of antioxidant on nanosilica and the aging resistance behavior in polypropylene

Jing Chen a,b, Ming Shu Yang b,, Shi Min Zhang b
a b

Polymers and Composites Division, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, China Beijing National Laboratory for Molecular Sciences, Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

a r t i c l e

i n f o

a b s t r a c t
Nanosilica was rstly reacted with the reactive antioxidant, methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (AO), via transesterication, to form a nanosilica-immobilized antioxidant, AO-silica. And then it was incorporated into polypropylene (PP) by melt compounding. Fourier transform infrared spectroscopy combined with the other characterization methods elucidated that the reactive antioxidant was chemically immobilized onto the nanosilica surface. SEM observation showed that the nanosilicaimmobilized antioxidant was homogeneously dispersed into the matrix of PP. It has been reported that the antioxidative efciency of AO-silica was superior to the corresponding low molecular counterpart (AO), based on the measurement of the oxidation induction time (OIT) of the PP/AO-silica and the PP/ AO compounds containing equivalent antioxidant component. By paying attention to the changes of carbonyl absorption at different UV exposure times, it was observed that the UV aging-resistance ability of PP/nanosilica-immobilized antioxidant was much higher than that of PP/neat nanosilica compound during the long-time accelerated photo aging. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 3 April 2010 Received in revised form 26 December 2010 Accepted 7 January 2011 Available online 15 January 2011 Keywords: A. Nano-structures B. Thermal properties D. Surface analysis

1. Introduction In the past decade, a lot of efforts have been made to produce a dramatic enhancement of polymers in physical, thermal, and mechanical properties. In order to obtain the excellent performance for required applications, additives are usually added into polymers, such as antioxidants, light stabilizers, thermal stabilizers, re retardants and antistatic agents. Hindered phenols are known to possess antioxidative properties and are therefore commonly used to retard oxidation in commercial plastics. Hindered phenol structures are often found in synthetic antioxidants and lead to the antioxidant effects of many natural compounds such as polyphenolic avonoids. The reactions between hindered phenol compounds and oxygen radicals have been thoroughly studied and the mechanisms of the hindered phenolic stabilization are well known [13]. However, the use of low molecular weight phenol antioxidants is always restricted because of two drawbacks: (1) they are easy to volatilize at high temperature during polymer processing; (2) they have low resistance to migration and extraction during the long-term service. So we use nanosilica-immobilized antioxidant to overcome these drawbacks. Polypropylene (PP) is known for widespread applications by its excellent mechanical properties with low cost and superior
Corresponding author. Tel./fax: +86 10 82615665.
E-mail address: (M.S. Yang). 1359-835X/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.compositesa.2011.01.006

processibility. However, the major drawback of PP is the degradation caused by light, heat, oxygen, humidity, and so on, during the processing and application periods [4,5]. Among the various factors, the photo-oxidation plays an important role. Exposure of unprotected and unlled PP to UV-irradiation in air produces rapid photo-oxidation with a marked effect on the mechanical and physical properties. Thus, the study of degradation and stability of PP is an extremely important scientic and industrial domain. The presence of bers or llers in a matrix PP might increase or decrease the rate of matrix degradation. Many researches on photo-degradation of PP/llers have been carried out [68]. Particularly, nanosilica has been widely used in polymers as inorganic ller to improve the properties of polymeric materials [914]. Recent studies show that nanosilica has been attracting increasing attention due to its fascinating properties and potential applications. Nanosilica is especially appealing to the modication with biomolecules to prepare medical diagnostics, biomolecule encapsulation, optical biosensor, etc. [1517], as they are stable in most solvent environments. Some research groups [1820] are devoted to preparing silica-supported catalysts by immobilizing catalysts onto the surface of nanosilica particles. In our previous work, reactive antioxidants were chemically immobilized onto the nanosilica surface with an aminosilane coupling agent [21]. According to what we have known in this eld, there have been no reports about immobilizing reactive antioxidants onto the surface of nanosilica particles to prepare silica-immobilized antioxidants without any


J. Chen et al. / Composites: Part A 42 (2011) 471477

coupling agent. Moreover, because of a lot of hydroxyl groups on the surface of nanosilica, the preparation of silica-immobilized antioxidants through transesterication is very simple, cheap and green. The aim of our study is to prepare a novel antioxidant using nanosilica as solid support to immobilize reactive antioxidant onto the surface and to evaluate the antioxidant efciency of the nanosilica-immobilized antioxidant in polypropylene, especially in a long-term accelerated photo aging test. Hence, the chemical immobilization of reactive antioxidant onto the surface of nanosilica particles has been investigated. The antioxidative efciency was evaluated by oxidative induction time (OIT) method. Accelerated ultraviolet aging experiments were carried out in an UV exposure instrument and the aging behavior was evaluated by FT-IR. 2. Materials and methods 2.1. Materials Fumed silica (Aerosil 200, average diameter = 12 nm, specic surface area = 200 25 m2/g) was obtained from Degussa-Hls and dried in a vacuum oven overnight at 105 C before use. The reactive antioxidant methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (AO, purity 99.8%) was purchased from TianJin ChenGuang Chemicals Co., Ltd. and used as-received. The unstabilized polypropylene (PP) powder was supplied by Yanshan Petrochemical Co. Ltd., Beijing, China. The melt ow index (MFI) is 24.0 g/ 10 min. Sodium methanol (CH3ONa) was obtained from Sinopharm Chemical Reagent Co., Ltd. All the solvents and reagents were of analytical grade and used as-received. 2.2. Preparation of AO-silica and PP/AO-silica nanocomposites The synthesis route is shown in Scheme 1. Methyl 3-(3,5-ditert-butyl-4-hydroxyphenyl) propionate (30 g) was melted at 70 C completely. Fumed nanosilica (1.0 g) was dispersed in the above solution. Catalyst CH3ONa (4.5, 5.5, 6.5, 7.5 wt.%) was added into the suspension respectively. The mixture was reuxed under stirring for 5 h, under N2 gas at 110 C. The product was ltered and then washed with anhydrous ethanol (200 mL, three times) and absolute methanol (200 mL, three times). The functionalized nanosilica (AO-silica) was dried in a vacuum oven overnight at 105 C. The PP/AO-silica nanocomposites were prepared by melt compounding method using a HAAKE Rheomix-600 internal mixer (Mess-Technic GmbH, Germany) at 180 C with a screw speed of 50 rpm for 5 min. Prior to the melt processing, the neat nanosilica and modied nanosilica were dried in a vacuum oven overnight at 105 C. The ratio of various components in PP/AO/SiO2 system is 50:0.1:2.5. And the content of inorganic component was xed at 5 wt.% in all the other samples of nanocomposites. The extruded pellets were pressed into lms with a thickness of 42 2 lm at

180 C for the FT-IR test. The prepared materials were pressed into sheets at 180 C with an average thickness of 260 lm and saved for DSC test. 2.3. Characterization The Fourier transform infrared spectra were recorded with KBr pellets on a PerkinElmer-System 2000 infrared spectrum analyzer in the wave-number range of 4000370 cm1. X-ray photoelectron spectroscopy (XPS) data were obtained with an ESCA-Lab220i-XL electron spectrometer from VG Scientic using 300 W Al Ka radiation. The base pressure is about 3 109 mbar. The binding energies are referenced to the C1s line at 284.6 eV from adventitious carbon. PerkinElmer TGA-7 was used to measure the thermal behavior of the PP/silica nanocomposites in nitrogen atmosphere from 50 C to 750 C at a heating rate of 20 C/min. Transmission electron microscope (TEM) images were obtained using a Hitachi (Japan) H-800 instrument with an accelerate voltage of 150 kV. The samples were dispersed in a few milliliters of ethanol in an ultrasonic bath. A droplet of this dispersion was placed on a copper grid which was covered with a carbon lm and the excess solution was subsequently removed by lter paper. Scanning electron microscope (SEM) images were taken on a JEOL S-4300F eld emission scanning electron microscope at 5 kV. Oxidation induction time (OIT) measurement was performed on a PerkinElmer DSC 7 according to the standard method (ISO 11357-6, 2002), which specied the gas ow and temperature ramping. The method used for the OIT test proceeded as follows. Firstly, the sample was held at 60 C for 5 min with a nitrogen ow of 50 mL/min. Subsequently, the sample was heated to 190 C at a rate of 20 C/min, still under a ow of nitrogen. After reaching 190 C, the sample was held for another 5 min, at which point the gas was switched to oxygen at a ow rate of 50 mL/min. The oxidation of the sample was observed as a sharp increase in heat ow due to the exothermic nature of the oxidation reaction. The OIT was obtained by the software of PerkinElmer DSC 7. Ultraviolet (UV) exposure tests were carried out in a WFH-201-B canned UV exposure instrument (Wenzhou Analytic Apparatus Co., China). The working temperature was controlled at 45 2 C and the wavelength of radiation was 300 nm. The rate of photo-oxidation of the UV degraded lms was followed by measuring carbonyl absorbance through FT-IR per 20 h upon UV exposure, for a period from 0 to 80 h. 3. Results and discussion 3.1. FT-IR spectroscopy Fig. 1 shows the FT-IR spectra of neat nanosilica and AO-silica. In the neat nanosilica, the broad strong bands around 3700 3200 cm1 are assigned to the OAH stretching vibration of silanol hydroxyls and adsorbed water, while the absorption at 1630 cm1 is assigned to the OAH bending of adsorbed water. In AO-silica (b e), absorption of SiAOAC at around 1086 cm1 is noticeable, which conrms chemical reaction between the carbomethoxy groups of reactive antioxidant and the OH groups on the silica surface. This result also indicates that the antioxidant has been anchored onto the nanosilica surface after the functionalization of nanosilica. Another obvious characteristic on AO-silica is the enhanced CH3 asymmetric stretch around 2978 cm1, which can be assigned to the tert-butyl groups of the hindered phenol antioxidant [15,22]. 3.2. Surface analysis X-ray photoelectron spectroscopy (XPS) technique is more surface sensitive than FT-IR and provides more information on the



neat nanosilica

CH3ONa 110

SiO2 O C


AO-silica AO
Scheme 1. Synthesis of AO-silica.

J. Chen et al. / Composites: Part A 42 (2011) 471477 Table 1 XPS analysis of carbon element of neat silica and AO-silica. Sample Neat silica Element C1s Position (eV) 284.80 286.43 287.42 284.78 286.52 287.80 284.58 286.70 288.00 284.68 286.85 288.54 Assignment



AO-silica (CH3ONa 0.0%)


AO-silica (CH3ONa 4.5%)


AO-silica (CH3ONa 6.5%)


Table 2 XPS analysis of oxygen element of neat silica and AO-silica. Fig. 1. FT-IR spectra of (a) neat silica, (bf) AO-silica (CH3ONa 0.0%, 4.5%, 5.5%, 6.5%, 7.5%, respectively). Sample Neat silica Element O1s Position (eV) 533.00 533.66 531.80 532.89 533.60 531.75 532.78 533.55 531.60 528.33 532.80 533.60 531.70 528.45 Assignment ASiAOASiA ACAO AC@O ASiAOASiA ACAO AC@O ASiAOASiA ACAO AC@O ASiAOACA ASiAOASiA ACAO AC@O ASiAOACA

chemical nature of the surface species. Fig. 2 shows the XPS survey spectrum for the surface of nanosilica and AO-silica. The photoelectron peaks for O1s, C1s and Si2p appear clearly at the binding energies of 533.0, 285.3 and 103.3 eV, respectively [23]. The comparison of the O1s and C1s binding energy in nanosilica and AO-silica is indicated in Tables 1 and 2. The binding energy 287.80, 288.00 and 288.54 eV were attributed to the characteristic of AC@O groups. The high binding energy 528.33 and 528.45 eV are assigned to the ASiAOAC groups in the AO-silica [24,25]. Especially, the binding energy of the ASiAOAC group was not observed when the AO-silica was prepared without catalyst of CH3ONa. It can be certied that AO and nanosilica have no chemical interactions but have the electrostatic adsorption only. Therefore, the XPS results further conrmed that the reactive antioxidant was chemically immobilized onto the surface of nanosilica particles through the carbomethoxy groups of AO anchored on nanosilica. 3.3. Microstructure analysis The morphologies of nanosilica before and after the reaction have been investigated by TEM observations, as shown in Fig. 3.

AO-silica (CH3ONa 0.0%)


AO-silica (CH3ONa 4.5%)


AO-silica (CH3ONa 6.5%)


It is observed that the aggregation of neat nanosilica (Fig. 3A) is largely reduced after surface reacted with the reactive antioxidant (Fig. 3BD). The neat nanosilica tends to form large aggregates and agglomerates because of the formation of hydrogen bonds between the abundant hydroxyl groups and adsorbed water on their surface. After reaction, the surface have turned from hydrophilic to hydrophobic, more compatible with the apolar polymer matrix, and thus reduced the aggregation of the nanoparticles. The dispersion states of neat nanosilica and AO-silica in polypropylene were evaluated in SEM observations, as shown in Fig. 4. Large and non-uniformly dispersed silica particles were observed in the PP/neat silica composite (Fig. 4A), with a particle size of 12 lm. It indicated that the aggregates and agglomerates of neat nanosilica were not dissociated by melt compounding. On the contrary, AO-silica, was homogeneously dispersed into the PP matrix on the nanometer scale (Fig. 4BD). It is due to the presence of organic molecules on the nanosilica particles, which turned the surface properties from hydrophilic to hydrophobic and then promote the uniform dispersion of nanoparticles in the PP matrix. The antioxidative efciency is related to the dispersion state of antioxidant in the polyolens. Hence, the homogenous dispersion of AOsilica will be effective to prevent the UV oxidative degradation of PP. 3.4. Thermal properties The results of the thermogravimetric analysis (TGDTG) of PP/ silica nanocomposites, in nitrogen atmosphere, are presented in Fig. 5 and Table 3. It was evident that the pure PP had a low decomposition temperature. The thermal stability of PP/AO and PP/SiO2 is little better than pure PP. This thermal stability was improved

Fig. 2. XPS proles of (a) neat silica, (b) AO-silica (CH3ONa 0.0%), (c) AO-silica (CH3ONa 4.5%), (d) AO-silica (CH3ONa 6.5%).


J. Chen et al. / Composites: Part A 42 (2011) 471477

Fig. 3. TEM images of (A) neat silica, (B) AO-silica (CH3ONa 0.0%), (C) AO-silica (CH3ONa 4.5%) and (D) AO-silica (CH3ONa 6.5%).

Fig. 4. SEM images of (A) PP/neat silica, (B) PP/AO-silica (CH3ONa 0.0%), (C) PP/AO-silica (CH3ONa 4.5%) and (D) PP/AO-silica (CH3ONa 6.5%).

when AO-silica was introduced. The nanocomposites of PP/AOsilica (CH3ONa 7.5%) had the best thermal stability than others, as had the highest loading of antioxidant on the AO-silica. The grafting yielding of AO-silica can be calculated according to the TGA analysis. And the exact loading data for various AO-silica have been listed in the Table 4. This may be due to the fact that the AO-silica has two promoting functions in the thermal stability of PP/AO-silica nanocomposite, one is its barrier effect which should improve the thermal

stability, and the other is the antioxidant effect towards the degradation of the polymer matrix which would increase the thermal stability. 3.5. The thermal oxidative of PP/silica nanocomposites Several PP/silica nanocomposites were prepared and their antioxidative behavior was evaluated by oxidation induction time (OIT) method. OIT is the time internal between the initiation of

J. Chen et al. / Composites: Part A 42 (2011) 471477


Fig. 6. Determination of OIT (DSC measurement, 190 C). (a) PP, (b) PP/SiO2, (c) PP/ AO, (d) PP/AO/SiO2, (ei) PP/AO-silica (CH3ONa 0.0%, 4.5%, 5.5%, 6.5%, 7.5%, respectively).

Fig. 5. TGA (A) and DTG (B) curves of (a) pure PP, (b) PP/SiO2, (c) PP/AO, (d) PP/AO/ SiO2, (ei) PP/AO-silica (CH3ONa 0.0%, 4.5%, 5.5%, 6.5%, 7.5%, respectively).

Table 3 TGA data of PP and PP/AO-silica composites in nitrogen atmosphere. Sample PP PP/SiO2 PP/AO PP/AO/SiO2 PP/AO-silica PP/AO-silica PP/AO-silica PP/AO-silica PP/AO-silica T5% (C) 401.1 402.0 402.8 403.7 406.0 408.3 413.3 416.0 416.1 T50% (C) 459.3 459.1 459.2 459.4 462.1 463.5 469.5 471.9 472.2 Tmax (C) 466.3 467.0 467.3 467.9 470.5 471.4 472.6 476.2 477.6

silica nanocomposites. Oxidation of pure PP and PP/SiO2 composite was detected immediately as the atmosphere was changed from nitrogen to oxygen. It shows that the neat nanosilica had little contribution to the OIT value of polypropylene. One reason for the shorter OIT of PP/AO compound could be the volatilization of antioxidant during the melt compounding because of its low molecular weight. That is to say, the antioxidant molecules immobilized onto nanosilica surface was not easy to volatilize at high temperatures. According to the DSC curves, the OIT value of PP/AO-silica (CH3ONa 4.5%) (0.4 min) is slightly higher than that of pure PP (0.2 min). And it can be obtained that the OIT value of PP/AO-silica (CH3ONa 7.5%) is 1 min, higher than those of pure PP and PP/AO/SiO2 compounds. The above results revealed that the AO-silica was more efcient than neat silica in preventing thermal oxidative degradation of PP nanocomposites. Obviously, the hindered phenol groups in AO-silica were most responsible for the exceptional antioxidant behavior. That is to say, this nanosilica-immobilized antioxidant could provide good antioxidant efciency when used as a stabilizer in polypropylene. 3.6. UV aging-resistance ability Fig. 7 shows the IR spectra of PP and PP/AO-silica at different aging times. A new broad band appeared at about 1715 cm1 after exposure, which belongs to a mixture of different carbonyl species [26]. The second new band at about 3400 cm1 belongs to hydroxyl group, which indicates the generation of hydroperoxide and hydroxyl species. In addition, the intensity of the carbonyl and hydroxyl bands grew with increasing exposure time. The increasing rate of these bands of PP/AO-silica was lower than those of pure PP. The IR spectra showed that the oxidation of pure PP is much more signicant than that of PP/AO-silica, and the addition of nano llers inhibited the oxidation of the matrix. Because of the similar spectrum of PP and PP/AO-silica after 80 h of exposure, the pure PP and PP/AO-silica might have the same photo-degradation mechanism. Since the presence of compatibilizer does not overlap the carbonyl region of products of the PP oxidation, the area of carbonyl band of FT-IR spectrum of each specimen can be obtained separately and considered as the quantity of the carbonyl [27,28]. It is the measure of photo-oxidative degradation of the samples. Fig. 8 shows a varying tendency of the area with exposure time about different samples. The area of the carbonyl region band could be seen as the quantity of the carbonyl. It is the measurement of photo-oxi-


0.0%) 4.5%) 5.5%) 6.5%) 7.5%)

Table 4 TGA data of AO + SiO2 in nitrogen atmosphere. Sample PP/AO-silica PP/AO-silica PP/AO-silica PP/AO-silica PP/AO-silica (CH3ONa (CH3ONa (CH3ONa (CH3ONa (CH3ONa 0.0%) 4.5%) 5.5%) 6.5%) 7.5%) Weight loss (wt.%) (200 C) 100.3 100.2 100.1 100.4 100.5 Weight loss (wt.%) (650 C) 98.4 95.3 94.8 93.7 93.0 AO content (wt.%) 1.9 4.9 5.3 6.7 7.5

oxygen ow and the onset of the oxidative reaction in the DSC testing. The more resistant the sample is to oxidative degradation, the longer the OIT value is. Fig. 6 shows the DSC curves of PP and PP/


J. Chen et al. / Composites: Part A 42 (2011) 471477

Fig. 7. Evolution of FT-IR spectra of (A) pure PP and (B) PP/AO-silica (CH3ONa 4.5%) at different UV exposure times (a) in the domain 38003050 cm1; (b) in the domain 19001500 cm1.

dative degradation of samples. It can be seen that the area of carbonyl bonds increases with increasing the UV aging time. The pure PP and PP/neat silica composite started to degradation not more than 20 h photo aging. The PP/AO-silica started to degrade at 20 h photo aging, but much slowly than the pure PP and PP/neat silica composite. Antioxidants are generally consumed by two methods. One is chemical loss due to their antioxidant action. The other is physical loss through volatilization or migration to the surroundings. The difference of AO and AO-silica in antioxidant efciency is mainly due to physical loss. The low molecular antioxidant is easy to volatilize or migrate from the matrix to the surroundings. Conversely, the antioxidant immobilized onto the nanosilica surface was no longer migratory and volatile in the PP matrix; thus the PP/AO-silica sample was more resistant to the photo-oxidation, especially during the long-term accelerated aging.

4. Conclusions
Fig. 8. Variation in the area of carbonyl band during the photo-degradation of PP thin lms. (a) PP, (b) PP/neat silica, (c) PP/AO, (d) PP/AO/SiO2, (ei) PP/AO-silica (CH3ONa 0.0%, 4.5%, 5.5%, 6.5%, 7.5%, respectively). The band range of carbonyl groups is in the domain 19001500 cm1.

In our study, we have demonstrated for the rst time that nanosilica could be utilized as an appropriate support for immobilization of antioxidant molecules. The reactive antioxidant was successfully immobilized onto the surface of nanosilica particles,

J. Chen et al. / Composites: Part A 42 (2011) 471477


which has been conrmed by several measurements. This nanosilica-immobilized antioxidant was homogeneously dispersed in the matrix of PP and showed improved antioxidative efciency in the nanocomposite. UV aging test of PP compounds was carried out in an UV exposure instrument. FT-IR results conrmed that the UV aging-resistance ability of PP/nanosilica-immobilized antioxidant was much higher than that of PP/neat silica compound during the long-time accelerated photo aging. Acknowledgment The authors are grateful for the support of the National Natural Science Foundation of China (Grant No.: 50533070). References
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