Kang I K, Ito Y, Sisido M, Imanishi Y
Department of Polymer Chemistry, Faculty of Engineering, Kyoto University, Japan.
Biomaterials. 1988 Jul;9(4):349-55. doi: 10.1016/0142-9612(88)90032-4.
A-B-A type block copolymers of poly(gamma-benzyl L-glutamate) (PBLG, A segment) and polydimethylsiloxane (PDMS, B segment) and PDMS (trunk)-PBLG (branch) graft copolymers were synthesized, and the permeation of oxygen in water and the permeation of oxygen and carbon dioxide in the dry state were investigated. The gas permeation coefficient (P) increased with increasing content of PDMS. However, PCO2/PO2 values of copolymer films were in the range 6-9, i.e. larger than 5.4 for PDMS film. The oxygen permeation in water suffered from the interfacial resistance, which was reduced by the hydrolysis of film surface. The Arrhenius plot of the gas permeation coefficient in the dry state of the block copolymer B showed a turning point at about 40 degrees C. This temperature is close to beta-peak temperature (39 degrees C) and may be ascribed to the molecular motion of the PBLG segment. Transmission electron microscopy showed that one of the block copolymer films (PDMS 46 mol%) appears to have PDMS segments dispersed in the PBLG matrix (island-in-sea structure) and one of the graft copolymer films (PDMS 58 mol%) appears to take a lamellar structure. The gas permeation across the graft copolymer film appears to occur through the continuous PDMS phase, leading to a near-negligible activation energy in this process.
合成了聚(γ-苄基-L-谷氨酸)(PBLG,A段)和聚二甲基硅氧烷(PDMS,B段)的A-B-A型嵌段共聚物以及PDMS(主干)-PBLG(支链)接枝共聚物,并研究了其在水中的氧气渗透以及在干燥状态下氧气和二氧化碳的渗透。气体渗透系数(P)随着PDMS含量的增加而增大。然而,共聚物薄膜的PCO2/PO2值在6-9范围内,即大于PDMS薄膜的5.4。水中的氧气渗透受到界面阻力的影响,而薄膜表面的水解降低了该阻力。嵌段共聚物B在干燥状态下气体渗透系数的阿伦尼乌斯曲线在约40℃处出现转折点。该温度接近β-峰值温度(39℃),可能归因于PBLG链段的分子运动。透射电子显微镜显示,其中一种嵌段共聚物薄膜(PDMS含量为46摩尔%)似乎具有分散在PBLG基质中的PDMS链段(海岛结构),而一种接枝共聚物薄膜(PDMS含量为58摩尔%)似乎呈现层状结构。气体透过接枝共聚物薄膜的渗透似乎是通过连续的PDMS相发生的,导致该过程中的活化能几乎可以忽略不计。