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Influence of monomer structure and dose rate on kinetic elements in electron-beam polymerizations
Radiation Physics and Chemistry ( IF 2.8 ) Pub Date : 2021-08-13 , DOI: 10.1016/j.radphyschem.2021.109737
Nicole L.K. Thiher 1 , Sage M. Schissel 2 , Julie L.P. Jessop 3
Affiliation  

In electron-beam (EB) polymerizations, altering the dose rate can cause property changes in the cured polymer, such as conversion, glass transition temperature (Tg), and physical or mechanical properties. These dose rate effects (DREs) complicate scale-up of EB polymerizations in industrial processes. A predictive relationship between DRE and changes in Tg was used to determine that DREs correlate to the number and lability of available bonds, not monomer size. Furthermore, the relationship between the primary radicals produced during EB irradiation and dose rate was explored via measurement of primary radical radiation chemical yield, G(R). Namely, G(R) is independent of dose rate, and instantaneous primary radical concentration is directly proportional to dose rate. Moreover, it was shown that non-reciprocity between dose rate and the rate of polymerization results in DREs. Future developments in radiation chemical yield measurements will aid in determining whether this disproportionality is due to the impact of dose rate on the concentration of propagating radicals or on the kinetic mechanism itself.



中文翻译:

单体结构和剂量率对电子束聚合动力学元素的影响

在电子束 (EB) 聚合中,改变剂量率会导致固化聚合物的性能发生变化,例如转化率、玻璃化转变温度 (T g ) 以及物理或机械性能。这些剂量率效应 (DRE) 使工业过程中 EB 聚合的放大变得复杂。DRE 和 T g变化之间的预测关系用于确定 DRE 与可用键的数量和不稳定性相关,而不是单体大小。此外,通过测量初级自由基辐射化学产率,探讨了 EB 照射过程中产生的初级自由基与剂量率之间的关系,(电阻). 即,(电阻)与剂量率无关,瞬时初级自由基浓度与剂量率成正比。此外,还表明剂量率和聚合率之间的非互易性导致了 DRE。辐射化学产率测量的未来发展将有助于确定这种不成比例是由于剂量率对传播自由基浓度的影响还是对动力学机制本身的影响。

更新日期:2021-08-20
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