自旋标记法研究STVPh/PEO共混体系的链运动

利用自旋标记法将氮氧自由基连接在聚氧化乙烯分子末端,测得其与不同羟基含量的苯乙烯-4-乙烯基苯酚共聚物组成高分子共混体系的ESR波谱,研究了各组分的分子链运动.自旋标记聚氧化乙烯的ESR谱图在整个温度范围内只显示快运动或慢运动的一种运动成分,表明氮氧自由基处于单一的环境中.高分子共混体系的ESR谱在一定温度范围内同时存在快运动和慢运动的两种运动成分,且两成分相对比例随温度的变化而变化,表明体系中氮氧自由基处于不同的微相环境中.由ESR谱得到的T_5mT,τ_c,E_a的值都随着体系中羟基含量的增加而变大,显示标记分子的链运动在共混体系中的活动逐步受阻.与此同时,随着该共混物中酚羟基和醚氧基间氢键相互作用强度的增大,共混物的相容性得到逐步改善.

A Study of the Chain Motion in STVPh/PEO System by ESR Spin Label

The electron spin resonance(ESR) spectra of PEO end labeled with nitroxide groups were recorded over a temperature range for the bulk polymer and for(1;3 by mass ratio) blends with styrene-vinylphenol copolymer(STVPh) containing different hydroxyl groups. For SLPEO, ESR spectra are composed of a single component, indicating the spin label locating in a single environment. For SP-1, SP-9 and SP-26 blends, two spectral components with different rates of motiona "fast" component and a "slow" component are observed in the experimental temperature range. It can be concluded that the fast and slow components should be attributed to micro heterogeneitYIN the blends: nitroxide radical trapped in the PEO rich and STVPh rich regimes in the blends, respectively. The miscibility of the blends increases with increasing hydrogen bonding density due to the specific interaction between hydroxyl groups in STVPh and the ether oxygen in PEO. Accordingly, the T_5mT, E_a, τ_c values are increased owing to the decrease of the SLPEO mobility of chain motion with increasing hindrance of physical cross-linking density.