Polymer of Intrinsic Microporosity Incorporating Thioamide Functionality: Preparation and Gas Transport Properties
Polymer of Intrinsic Microporosity Incorporating Thioamide Functionality: Preparation and Gas Transport Properties
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DOI：
10.1021/ma200918h
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发表时间：
2011-08-23
期刊：
影响因子：
5.5
通讯作者：
Jansen, Johannes C.
中科院分区：
文献类型：
--
作者：
Mason, Christopher R.;Maynard-Atem, Louise;Jansen, Johannes C.
以五硫化二磷为硫化剂，在亚硫酸钠存在下对PIM-1进行后改性，制备了一种新型的具有固有微孔结构的聚合物硫代酰胺-PIM-1。首先在低分子量模型化合物3，13-二氰基苯并-1，2，4 '，5'-双（1，4-苯并二氧六环）上测试了该化学。对于聚合物，实现了高达80%的腈向硫代酰胺的转化率。改性导致聚合物的BET表面积降低，从母体PIM-1的770 m（2）g（-1）降低到80%腈转化为硫代酰胺时的263 m（2）g（-1）。改性后，聚合物不再溶于氯化溶剂如CHCl（3），但溶于极性非质子溶剂如THF、DMF、DMSO和DMAc。从THF浇铸硫代酰胺-PIM-1的自支撑膜。单一气体渗透性测量显示，与母体聚合物相比，选择性增加，但渗透性降低。乙醇处理，去除闭塞的THF以及提高自由体积，对膜渗透性有显着的影响。对于所制备的膜，理想的CO（2）/N（2）选择性为38.5，CO（2）渗透率为150 barrer。乙醇处理使CO（2）渗透率增加到1120 barrer，CO（2）/N（2）理想选择性降低到30.3。
A novel polymer of intrinsic microporosity, thioamide-PIM-1, has been prepared by postmodification of PIM-1, using phosphorus pentasulfide as a thionating agent in the presence of sodium sulfite. The chemistry was first tested on a low molecular weight model compound, 3,13-dicyanobenzo-1,2,4',5'-bis(1,4-benzodioxane). For the polymer, up to 80% conversion of nitrile to thioamide was achieved. Modification leads to a reduction in the BET surface area of the polymer, from 770 m(2) g(-1) for the parent PIM-1 to 263 m(2) g(-1) on 80% conversion of nitrile to thioamide. After modification, the polymer is no longer soluble in chlorinated solvents such as CHCl(3), but is soluble in polar aprotic solvents such as THF, DMF, DMSO, and DMAc. Self-supported membranes of thioamide-PIM-1 were cast from THF. Single gas permeability measurements showed increased selectivities but reduced permeabilities compared to the parent polymer. Ethanol treatment, which removes occluded THF as well as enhancing free volume, has a pronounced effect on membrane permeability. For the as-prepared membrane, an ideal CO(2)/N(2) selectivity of 38.5 was achieved with a CO(2) permeability of 150 barrer. Ethanol treatment increased the CO(2) permeability to 1120 barrer, with a decrease in CO(2)/N(2) ideal selectivity to 30.3.