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Temperature dependence of structural alteration by ultraviolet irradiation in acrylic-urethane coatings studied by positron annihilation spectroscopy and solvent swelling behavior
Polymer Degradation and Stability ( IF 5.9 ) Pub Date : 2019-02-08 , DOI: 10.1016/j.polymdegradstab.2019.02.007
Takato Ishida , Ryoma Kitagaki , Shogo Yamane , Hideaki Hagihara

The structural alteration of acrylic-urethane coatings, induced by photo-aging, and its temperature dependence, was investigated using positron annihilation lifetime spectroscopy and solvent swelling experiments. The results revealed a slight structural alteration due to photo-aging at 20 °C. On the other hand, a significant structural alteration occurred due to photo-aging at 60 °C, which resulted in a decrease in the pore size and total pore volume. To study the mechanism of such morphological changes, infrared spectra were measured before and after aging the samples. The results revealed the breakage of the urethane crosslink points and the generation of various photo-products including peroxide species that can form hydrogen bonds. This indicates the foundation of new physical and chemical crosslinks (different from the initial urethane linkage). Based on the chemical modifications, probable mechanisms of the internal morphological changes are proposed. Moreover, the changes are mainly due to an enhancement in the chain-mobility, due to the destruction of the polymer network and an increase in the inter-chain interactions. The results of this study reveal that significant internal structural alterations can occur after sufficient damage to the initial network structure. The proposed explanation is reasonable in relation to the temperature dependence of photo-induced structural alterations, and with respect to the molecular mobility and reaction ratio of photo-oxidation.



中文翻译:

用正电子an没光谱研究丙烯酸-聚氨酯涂料中紫外线辐射的结构变化与温度的关系以及溶剂溶胀行为

使用正电子an没寿命谱和溶剂溶胀实验研究了光老化引起的丙烯酸-氨基甲酸酯涂层的结构变化及其温度依赖性。结果表明,由于在20°C下的光老化,结构略有变化。另一方面,由于在60℃下的光老化,发生了显着的结构改变,这导致孔径和总孔体积的减小。为了研究这种形态变化的机理,在老化样品之前和之后测量了红外光谱。结果揭示了氨基甲酸酯交联点的断裂以及各种光产物的产生,包括可以形成氢键的过氧化物。这表明了新的物理和化学交联的基础(与最初的氨基甲酸酯键不同)。基于化学修饰,提出了内部形态变化的可能机理。而且,这些变化主要是由于聚合物网络的破坏和链间相互作用的增加引起的链迁移性的增强。这项研究的结果表明,在对初始网络结构进行充分破坏之后,可能会发生重大的内部结构变化。所提出的解释在光致结构改变的温度依赖性以及光氧化的分子迁移率和反应比方面是合理的。提出了内部形态变化的可能机制。而且,变化主要是由于聚合物网络的破坏和链间相互作用的增加,链迁移率的提高。这项研究的结果表明,在对初始网络结构进行充分破坏之后,可能会发生重大的内部结构变化。所提出的解释在光致结构改变的温度依赖性以及光氧化的分子迁移率和反应比方面是合理的。提出了内部形态变化的可能机制。而且,变化主要是由于聚合物网络的破坏和链间相互作用的增加,链迁移率的提高。这项研究的结果表明,在对初始网络结构进行充分破坏之后,可能会发生重大的内部结构变化。所提出的解释在光致结构改变的温度依赖性以及光氧化的分子迁移率和反应比方面是合理的。这项研究的结果表明,在对初始网络结构进行充分破坏之后,可能会发生重大的内部结构变化。所提出的解释在光致结构改变的温度依赖性以及光氧化的分子迁移率和反应比方面是合理的。这项研究的结果表明,在对初始网络结构进行充分破坏之后,可能会发生重大的内部结构变化。所提出的解释在光致结构改变的温度依赖性以及光氧化的分子迁移率和反应比方面是合理的。

更新日期:2019-02-08
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