磺酸基功能化有机聚苯乙烯/无机磷酸氢锆催化环氧大豆油
Sulfonic-Functionalized Organic Polystyrene/Inorganic Hydrogen Zirconium Phosphate Catalyzed Epoxidation of Soybean Oil
作者单位E-mail
邹晓川 重庆第二师范学院生物与化学工程学院, 重庆 400067  
黄林玉 重庆第二师范学院生物与化学工程学院, 重庆 400067  
全纹萱 重庆第二师范学院生物与化学工程学院, 重庆 400067  
王存 重庆第二师范学院生物与化学工程学院, 重庆 400067  
王跃 重庆第二师范学院生物与化学工程学院, 重庆 400067  
赵欣 重庆第二师范学院, 重庆市功能性食品协同创新中心, 重庆 400067 zhaoxin@cque.edu.cn 
谭脂文 重庆师范大学化学学院, 重庆 401331  
摘要: 首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化剂催化合成环氧化大豆油的催化性能。结果表明:以叔丁基过氧化氢(TBHP)为氧化剂,固体催化剂对大豆油的环氧反应具有良好的催化性能,相比于催化剂1(磺酸化低聚苯乙烯基膦酸-磷酸氢锆),在相同的条件下,催化剂2(磺酸化聚(苯乙烯-苯乙烯膦酸)-磷酸氢锆)表现出更高的催化活性(产率:58.6% vs 53.3%),这主要归因于催化剂2拥有更大的比表面积、孔容以及孔径,为底物和催化剂的接触提供足够的催化场所。催化剂2重复使用7次后,催化活性未见明显降低。第8次反应结束后,将其置于2 mol·L-1稀盐酸中静置过夜后,在进行第9和10次循环时,催化活性又得以恢复。
关键词: 有机聚苯乙烯/无机磷酸氢锆  磺酸功能化  非均相催化  氧化
基金项目: 重庆市基础与前沿研究项目(No.cstc2018jcyjAX0110)、重庆市教育委员会科学技术研究项目(No.KJQN201801607,KJQN201801602)、重庆高校创新团队建设计划资助项目(No.CXTDX201601040)、重庆第二师范学院绿色合成及分析检测重点实验室项目(No.2016kjpt08)以及重庆第二师范学院青年人才项目(No.160921zt)资助。
Abstract: Two kinds of sulfonic-fictionalized organic polystyrene/inorganic zirconium hydrogen phosphate heterogeneous catalysts were firstly prepared. The catalysts were characterized by Fourier infrared spectroscopy (FT-IR), N2 adsorption-desorption test, X-ray diffraction (XRD) and scanning electron microscope (SEM). A possible model of the catalyst was proposed. Secondly, the catalytic performance of heterogeneous catalysts was investigated in the epoxidation of soybean oil. The results showed that the heterogeneous catalysts could effectively catalyze epoxidation of soybean oil with tert-butyl hydroperoxide (TBHP) as oxidant. Compared with catalyst 1 (sulfonic-functionalized zirconium oligo-polystyrenyl phosphonate-phosphate), catalyst 2 (sulfonic-functionalized zirconium poly(styrene-phenylvinylphosphonate)-phosphate) showed higher catalytic activity under the same conditions (Yield:58.6% vs 53.3%). It is mainly attributed to the larger specific surface area, pore volume and pore size of catalyst 2, which provides sufficient catalytic sites for substrate and catalyst contact. Finally, after repeated use for 7 times of the catalyst 2, there was no significant decrease in catalytic activity. Interestingly, after the end of the 8th reaction, the catalyst was allowed to stand in 2 mol·L-1 dilute hydrochloric acid for overnight, and the catalytic activity was restored again at the 9th and 10th cycle.
Keywords: organic polystyrene/inorganic zirconium hydrogen phosphate  sulfonic-functionalized  heterogeneous catalysis  oxidation
投稿时间:2018-11-07 修订日期:2019-06-03
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邹晓川,黄林玉,全纹萱,王存,王跃,赵欣,谭脂文.磺酸基功能化有机聚苯乙烯/无机磷酸氢锆催化环氧大豆油[J].无机化学学报,2019,35(8):1349-1356.
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