一种后交联大孔吸附树脂的合成及其对苯酚和维生素B_(12)吸附性能研究  

PREPARATION OF A POST-CROSSLINKED MACRORETICULAR RESIN ADSORBENT AND ITS ADSORPTION PERFORMANCE ON PHENOL AND VB_(12)

作　　者：曾小伟[1] 陈丽娟[1] 范云鸽[1] 王春红[1] 施荣富[1] 

机构地区：[1]功能高分子材料教育部重点实验室南开大学高分子化学研究所,天津300071

出　　处：《高分子学报》2009年第9期909-916,共8页Acta Polymerica Sinica

基　　金：天津市自然科学基金(基金号09JCYBJC13600)资助项目;天津市科技攻关计划培育项目(项目号06YFGPSH02800)资助

摘　　要：工业二乙烯苯悬浮聚合制备的大孔树脂,在二氯乙烷溶剂中以无水三氯化铁为催化剂进行悬挂双键后交联反应,得到的后交联树脂的比表面积和孔容都有显著增加.低温氮气吸附/脱附等温线得到的孔径分布曲线证明初始共聚物PDT-55(polydivinylbenzene,toluene as porogen)和PDH-55(polydivinylbenzene,heptane andtoluene as porogen)经后交联反应,所形成的新孔以微孔为主.树脂对水溶液中苯酚和维生素B12(VB12)的静态吸附研究发现树脂经后交联后,对苯酚的吸附量有显著提高,但对VB12的吸附量增加不大,原因是分子尺寸较大的VB12无法进入由悬挂双键后交联反应所形成的微孔.树脂PDT-55pc对苯酚的吸附量大于商品树脂XAD-4;后交联前后树脂PDT-55、PDT-55pc(post-crosslinking of PDT-55)、PDH-55、PDH-55pc(post-crosslinking ofPDH-55)对VB12的吸附量均大于树脂XAD-4.在本研究的实验条件下,Langmiur和Freundlich吸附等温线方程能很好地拟合树脂对水溶液中苯酚和VB12的吸附,相关系数在0.99以上.静态吸附动力学实验结果表明后交联前后树脂对苯酚的吸附较VB12更容易达到吸附平衡.吸附动力学数据的拟合结果显示,McKay二级吸附动力学模型符合树脂对苯酚的吸附,而对VB12的吸附更符合Lagergren一级吸附动力学模型.A post-crosslinked polymeric adsorbent was prepared by Friedel-Crafts reaction of the pendant vinyl groups. It was obvious that both the specific surface area and the pore volume of starting copolymers increased significantly after post-crosslinking. Nitrogen adsorption/desorption isotherms and pore size distribution curves revealed that the new pores of the resulted copolymers formed by post-crosslinking reaction were mainly micropores. The results of static adsorption indicated that the adsorbents sorption capability of phenol had been greatly improved after post-crosslinked, while this phenomenon was not obvious to VB12 . It could be attributed to the molecular size of VB12 ,which prevented VB12 diffusing from solution phase into the micropore region formed by post-crosslinking. PDT-55pe exhibited higher adsorption capacity of phenol than the commercial maeroporous resin XAD-4. The adsorption capacity of VB12 onto adsorbent PDT-55 （ polydivinylbenzene, toluene as porogen ）, PDT-55pc （ posterosslinking of PDT-55）, PDH-55 （polydivinylbenzene, heptane and toluene as porogen）, PDH-55pc （postcrosslinking of PDH-55 ） was larger than that onto XAD-4. The equilibrium adsorption curves for resins adsorbed phenol and VB12 showed good agreement with the Langmuir and Freundlich isotherm equations. Correlation coefficients were larger than 0.99. Adsorption kinetic curves indicated that the time for adsorption equilibrium of phenol was shorter than that of VB12 . The kinetic data were then fitted to the pseudo-first order and pseudo-second order models. The results showed that phenol uptake onto adsorbents could be followed by the pseudo-second order model, while VB12 onto adsorbents would be more suitably represented by the pseudo-first order model.

关 键 词：聚二乙烯苯树脂 悬挂双键 后交联 吸附 

分 类 号：O647.31[理学—物理化学] O631.3[理学—化学]