Synthesis and gas permeability of membranes of Poly(vinyl ether)s bearing oxyethylene segments
Synthesis and gas permeability of membranes of Poly(vinyl ether)s bearing oxyethylene segments
复制标题
DOI：
10.1016/j.polymer.2012.02.036
复制
发表时间：
2012-04
期刊：
影响因子：
4.6
通讯作者：
T. Sakaguchi;M. Ohashi;K. Shimada;T. Hashimoto
中科院分区：
文献类型：
--
作者：
T. Sakaguchi;M. Ohashi;K. Shimada;T. Hashimoto
将乙烯基醚单体[2-甲氧基乙基乙烯基醚：MOVE，2-(2-甲氧基乙氧基)乙基乙烯基醚：乙基，2-金刚烷基乙烯基醚：ADVE，2-(2-乙氧基乙氧基)甲基丙烯酸乙酯：VEEM]进行阳离子共聚合，得到了三种不同组成比的乙烯基醚共聚物[聚(MOVE-ADVE)S、聚(MEVE-ADVE)S和聚(MEVEV-VEEM)S]。当单体投料比为1：1时，聚(Move-AdVE)和聚(甲基-AdVE)的玻璃化转变温度(Tg)分别为55℃和28℃，但当AdVE的投料比降低时，共聚物的玻璃化转变温度(Tg)接近或低于室温。室温以上的聚(MOVE-ADVE)S和聚(MEVE-ADVE)从甲苯溶液中浇铸得到了自支撑膜。它们具有较高的CO2渗透性和较高的CO2/N2分离系数(P(CO2)n=0.22-36桶，P(CO2)/P(N_2)n=0.19-40)。无论单体投料比如何不同，聚(甲基-乙烯-乙烯-乙二醇酯)S的玻璃化转变温度都很低，约为−70℃左右。甲基丙烯酸酯基团在聚(甲基丙烯酸甲酯)S中，在加热条件下发生部分反应，制得交联聚合物膜。交联膜表现出较高的CO_2/N_2选择性，特别是具有最高MEVEV比率的聚(MEVE-VEEM)膜具有较高的CO_2透过率和高选择性(P(CO_2)=(120)巴，P(CO_2)/P(N_2)(==0.55))。
Cationic copolymerizations of vinyl ether monomers [2-methoxyethyl vinyl ether: MOVE, 2-(2-methoxyethoxy)ethyl vinyl ether: MEEVE, 2-adamantyl vinyl ether: AdVE, 2-(2-vinyloxyethoxy)ethyl methacrylate: VEEM] were performed to obtain three types of vinyl ether copolymers [poly(MOVE-AdVE)s, poly(MEEVE-AdVE)s, and poly(MEEVE-VEEM)s] with different composition rates. Poly(MOVE-AdVE) and poly(MEEVE-AdVE) obtained at monomer feed ratio of 1:1 exhibited the glass transition temperatures (Tg) of 55 and 28 °C, respectively, but the Tg's of copolymers were near or lower than room temperature when the feed ratio of AdVE decreased. Poly(MOVE-AdVE)s and poly(MEEVE-AdVE) with Tg's above room temperature afforded free-standing membranes by casting them from toluene solutions. They exhibited relatively high CO2permeability and high CO2/N2separation factors (P(CO2) = 22–36 barrers, P(CO2)/P(N2) = 19–40). The Tg's of poly(MEEVE-VEEM)s were very low and around −70 °C irrespective of the difference of monomer feed ratio. Methacrylate groups in poly(MEEVE-VEEM)s partially reacted under heating to give crosslinked polymer membranes. The crosslinked membranes showed high CO2/N2selectivity, especially the poly(MEEVE-VEEM) membrane possessing the highest ratio of MEEVE exhibited high CO2permeability and high selectivity (P(CO2) = 120 barrers, P(CO2)/P(N2) = 55).