Lu Ying, Wang Yaotao, Fu Lianlian, Jiang Zhiyong, Men Yongfeng
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, Renmin Street 5625, 130022 Changchun, P. R. China.
J Phys Chem B. 2014 Nov 13;118(45):13019-23. doi: 10.1021/jp5093702. Epub 2014 Oct 31.
Crystalline lamellar thickness in syndiotactic polypropylene (sPP) during crystallization from either isothermal molten or stretching induced localized melt states and during subsequent heating was investigated by means of temperature dependent small-angle X-ray scattering techniques. Well-defined crystallization lines where the reciprocal lamellar thickness is linearly dependent on crystallization temperature were observed. Unlike in the case of polybutene-1 where stretching crystallization line was shifted to direction of much smaller lamellar thickness (Macromolecules 2013, 46, 7874), the stretching induced crystallization line for sPP deviates from its corresponding isothermal crystallization line only slightly. Such phenomenon could be attributed to the fact that both crystallization processes from quiescent melt and stress induced localized melt are mediated in a mesomorphic phase in sPP. Subsequent heating of sPP after crystallization revealed the same melting behavior in both systems for the two kinds of crystallites obtained from either quiescent melt or stretching induced localized melt. Both of them underwent melting and recrystallization when the lamellar thickness was smaller than a critical value and melting directly without changing in thickness when the lamellar thickness was larger than the critical value. The melting behavior in sPP systems can be understood by considering the chain relaxation ability within crystalline phase and also can be used as evidence that the crystallization from molten state and stress-induced crystallization passed through the intermediate phase before forming crystallites.
通过温度相关的小角X射线散射技术,研究了间规聚丙烯(sPP)在等温熔融结晶或拉伸诱导的局部熔融状态下以及随后加热过程中的结晶层片厚度。观察到了明确的结晶线,其中层片厚度的倒数与结晶温度呈线性关系。与聚丁烯-1的情况不同,聚丁烯-1的拉伸结晶线向小得多的层片厚度方向移动(《大分子》2013年,第46卷,第7874页),sPP的拉伸诱导结晶线仅略微偏离其相应的等温结晶线。这种现象可归因于以下事实:sPP中从静态熔体结晶和应力诱导的局部熔体结晶这两个过程都是在介晶相中进行的。sPP结晶后的后续加热显示,对于从静态熔体或拉伸诱导的局部熔体获得的两种微晶,两个系统中的熔融行为相同。当层片厚度小于临界值时,它们都经历了熔融和再结晶;当层片厚度大于临界值时,它们直接熔融且厚度不变。sPP系统中的熔融行为可以通过考虑晶相内的链松弛能力来理解,也可以作为从熔融态结晶和应力诱导结晶在形成微晶之前经过中间相的证据。