竹粉接枝改性提高竹塑复合材料的力学性能
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国家自然科学基金资助项目(31170535,30771683)。


Bamboo flour modifying by grafted improves mechanical property of bamboo-plastic composites
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    摘要:

    为提高竹粉与聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(polyethylene terephthalate glycol,PETG)基体的界面结合力,拓宽其应用领域,该论文以2-溴异丁酰溴修饰过的竹粉为大分子引发剂,FeCl3·6H2O/三苯基膦为催化体系,抗坏血酸为还原剂,采用电子活化再生原子转移自由基聚合法在竹粉表面接枝聚甲基丙烯酸甲酯,并通过红外光谱分析竹粉改性前后的表面化学基团变化。利用熔融共混、模压成型方法制备竹粉/PETG竹塑复合材料。研究了竹粉接枝前后竹塑复合材料的弯曲性能,考察了竹粉改性对竹塑复合材料动态热力学性能的影响,并利用环境扫描电镜对竹粉/PETG复合材料冲击断面进行观察。研究结果表明:接枝前后竹粉的红外光谱的显著变化证实了接枝反应的发生,聚甲基丙烯酸甲酯(polymethyl methacrylate,PMMA)成功地接枝到竹粉表面;与未改性的竹粉相比,改性后竹粉填充PETG复合材料的弯曲性能有较大提高,如竹粉质量分数为30%复合材料改性后弯曲强度提高了16%;动态热机械分析可知,竹粉经改性后其复合材料玻璃化转变温度和损耗角正切均有所降低,且在升温过程中仅出现一个损耗峰,表明竹粉表面接枝的PMMA可以充当竹粉与PETG的增容剂;环境扫描电子显微镜显示,竹粉经接枝改性后,竹粉能均匀分散在PETG基体中,竹粉与PETG基体之间的相容性得到了有效改善,界面结合良好。研究结果对通过竹粉表面处理提高竹粉/PETG竹塑复合材料的性能有重要的实际意义。

    Abstract:

    Abstract: In order to improve the interfacial bonding strength of bamboo flour and polyethylene terephthalate glycol (PETG) matrix and broaden the application fields of bamboo flour filled PETG composites, in this study, we applied the method of AGET (activators generated by electron transfer) ATRP (atom transfer radical polymerization), and straightforwardly grafted methyl methacrylate (MMA) from the bamboo flour surface using the 2-bromoisobutyryl bromide (BIBB) functionalized bamboo flour as a macro-initiator, FeCl3·6H2O as the catalyst, triphenylphosphine (PPh3) as the ligand, and ascorbic acid as the reducing agent. And then Fourier transform infrared spectroscopy (FTIR) was used to examine the changes of surface groups before and after modification. Simultaneously, the bamboo flour filled PETG composites were prepared by a melt blending and compression molding process. The flexural properties of bamboo flour/PETG composites were investigated, and the impact fractured surfaces of unmodified and modified bamboo flour filled PETG composites were observed by an environmental scanning electronic microscopy micrograph (ESEM) in succession. In addition, the effect of the grafted bamboo flour on the dynamic thermal mechanical properties (storage modulus E', glass transition temperature Tg, and loss tangent tanδ) of bamboo flour/PETG composites was also investigated. The results showed that the obvious variety of FTIR of the bamboo flour after grafting modification (the intensities of the bands at 1732 cm-1 strengthened and the peak at 3000 and 2954 cm?1 appeared in the spectra of grafted substrates) confirmed that the grafting reaction had taken place; and PMMA was successfully grafted onto the bamboo flour surfaces. The flexural tests showed that the flexural properties of the grafted bamboo flour filled PETG composites were better than those of unmodified ones. When the grafted bamboo flour content was 30%, the flexural strength of the composite increased 16%, compared to bamboo flour/PETG composites of an equal amount of unmodified bamboo flour. This fact shows that the grafting modification of bamboo flour by coating a layer of PMMA is an effective method to improve internal bond strength between bamboo flour and PETG matrix. Furthermore, a dynamic mechanical analysis (DMA) and morphology observations well substantiated the above-mentioned mechanical results. The results of a dynamic mechanical analysis (DMA) showed that the peak value of tanδ decreased and the glass transition temperature (the position of the maximum in tanδ) decreased after grafting modification. Comparing with the corresponding tanδ curves of the composites, it was also found that the curves of the grafted bamboo flour filled PETG composites appeared to exhibit only one peak during the heating process. This result suggests that PMMA could act as a compatibilizer to enhance the interfacial compatibility between bamboo flour and a PETG matrix. From the impact fracture morphologies of ESEM, it can be concluded that the bamboo flour exhibits good dispersion in a PETG matrix after grafting modification, i.e., the grafted bamboo flour had better interfacial compatibility with a PETG matrix than unmodified ones, and interface bonding between grafted bamboo flour and a PETG matrix was good. The research results in this paper have great practical significance on improving the properties of bamboo flour/PETG bamboo-plastic composites by a bamboo flour surface treatment.

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余方兵,宋剑斌,吴秋宁,陈丽红,杨文斌.竹粉接枝改性提高竹塑复合材料的力学性能[J].农业工程学报,2013,29(23):79-85. DOI:10.3969/j. issn.1002-6819.2013.23.011

Yu Fangbing, Song Jianbin, Wu Qiuning, Chen Lihong, Yang Wenbin. Bamboo flour modifying by grafted improves mechanical property of bamboo-plastic composites[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE),2013,29(23):79-85. DOI:10.3969/j. issn.1002-6819.2013.23.011

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  • 收稿日期:2013-05-15
  • 最后修改日期:2013-10-23
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  • 在线发布日期: 2013-11-07
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