Synthesis of the Permselective Polymer Thin Films by Plasma Polymerization Method and its Application to the Separation Technology

研究了等离子体聚合制备适用于分离过程的有机薄膜。首先，在气体分离膜的情况下，使用的两种单体是六甲基二硅氧烷（HMDS）和六氟苯（HFB）。等离子体聚合膜沉积在微孔VS，聚砜中空纤维和多孔陶瓷基板。研究了等离子体聚合薄膜的聚集态结构和渗透性能随放电能量W/FM、衬底温度和沉积后退火时间的变化规律，其中W、F和M分别为射频功率、单体流速和单体分子量。利用热重分析、红外光谱、光电子能谱等手段对薄膜的化学结构和聚集态结构进行了研究。随着W/FM值的增加，由不饱和键或芳香基团组成的粗糙结构转变为高度交联的网络结构。通过等离子体聚合膜的气体分离因子的大小随着交联度的增加而增加。通过等离子体聚合的HFB（PHFB）膜的氧气渗透系数几乎保持恒定，约为2.8 × 10^（-8）> <cm ^3>（STP）/cm。在283 K时，随着温度的升高，来自氮气的秒·cm Hg从4.5的量级逐渐降低。这些结果表明，PHFB膜是有利的膜用于富氧。研究还发现，等离子体聚合的HMDS膜适用于氢分离膜。其次，作为研究通过等离子体处理在基底表面引入络合基团的第一步，合成了磷盐并用于萃取阴离子金属配合物。因此，发现这些试剂适用于金属离子的萃取和分离。

Plasma polymerization was studied to synthesize the organic thin films which is applicable to the separation processes. At first, in the case of gas separation membranes, two kinds of monomers used were hexamethyldisiloxane (HMDS), and hexafluorobenzene (HFB). Plasma polymerized films were deposited on the substrates of Millipore VS, polysulfone hollow fibers and porous ceramics. The aggregation structures and permeation properties of plasma-polymerized thin films were investigated as functions of the discharge energy W/FM, the substrate temperature and the annealing time after deposition, where W,F, and M are the RF power, the monomer flow rate and the molecular weight of monomer, respectively. The chemical and aggregation structures of the films were investigated on the basis of TG, FT-IR, and ESCA. The rough structure composed of unsaturated bond or aromatic group changed into the highly cross-linked network structure with increases in the W/FM value. The magnitude of gas separation factor through the plasma-polymerized-film increased with an increase in the degree of crosslinking. The oxygen permeability coefficient through the plasma-polymerized HFB (PHFB) film remained almost constant at about 2.8 x <10^(-8)> <cm^3> (STP)/cm. sec.cmHg from nitrogen decreased gradually from the magnitude of 4.5 at 283 K with an increase in temparature. These results shows that the PHFB film is advantageous for the membrane for oxygen enrichment. It was also found that the plasma-polymerized HMDS film was suitable for the hydrogen separation membrane. Secondarily, as the first step of investigation for introducing complexing groups onto the surface of substrates by plasma-treatment, the phosphonium salts were synthesized and used to extract anionic metal complexes. Consequently, it was found that these reagents are suitable for extraction and separation of metal ions.