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Structure-reactivity studies on the polymerization and crosslinking behavior of tri(propylene glycol) diacrylate in aqueous solutions

机译:三丙烯酸丙二醇酯在水溶液中聚合和交联行为的结构反应性研究

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Radiation induced polymerization of tri(propylene glycol) diacrylate (TRPGDA) has been investigated by steady state and pulse radiolysis (PR) techniques. Reactions of TRPGDA with primary species of water radiolysis such as OH radical, e_(aq)~-, H atom and oxidizing species like N_3~· are reported. The rate constant values of 2.9 ± 0.19 x 10~9 dm~3 mol~(-1) s~(-1) and 1.3 x 10~9 dm~3 mol~(-1) s~(-1) were obtained for the reaction of TRPGDA with e_(aq)~- and OH radical, respectively. The spectrum of hydrated electron was found to be pH dependent whereas the spectrum of transient species formed with OH radicals was found to be unaffected with pH variation. The radical anion formed, preferentially undergoes propagation. The OH adduct was found to be an α-carboxyalkyl radical with an absorption maximum at 300 nm. Steady state investigation reveals a significant dependence of the polymerization behavior on the nature of radiolytic species present and on the ambient environment. A very efficient function of TRPGDA as a crosslinker in poly(vinyl alcohol) matrix was demonstrated by the reduction in D_(gel) value from 1.1 kGy to 0.2 kGy for crosslinking in presence of 1% TRPGDA.
机译:已通过稳态和脉冲辐射分解(PR)技术研究了三丙烯酸丙二醇酯(TRPGDA)的辐射诱导聚合。报道了TRPGDA与水辐射分解的主要物种如OH自由基,e_(aq)〜-,H原子和氧化性物种如N_3〜·的反应。获得的速率常数值为2.9±0.19 x 10〜9 dm〜3 mol〜(-1)s〜(-1)和1.3 x 10〜9 dm〜3 mol〜(-1)s〜(-1)分别使TRPGDA与e_(aq)〜-和OH自由基反应。发现水合电子的光谱是pH依赖性的,而发现由OH基形成的瞬态物质的光谱不受pH变化的影响。形成的自由基阴离子优先扩散。发现该OH加合物是在300nm处具有最大吸收的α-羧烷基。稳态研究表明,聚合反应行为对存在的放射性物质的性质和周围环境有很大的依赖性。通过在1%TRPGDA存在下进行交联将D_(gel)值从1.1 kGy降低至0.2 kGy,证明了TRPGDA作为聚乙烯醇基质中交联剂的非常有效的功能。

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