Fu Peng, Huo Jiaxin, Li Jingqing, De Rosa Claudio, Jiang Shichun
School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China.
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Monte Sant'Angelo, Via Cintia, 80126 Napoli, Italy.
Soft Matter. 2024 Apr 3;20(14):3191-3202. doi: 10.1039/d4sm00152d.
Different polymer chains in a solution or melt have different conformations with corresponding entropy at each moment, which would be confined after crystallization. Equilibrium concept-based conformation or conformational entropy depends on chain dynamics, which is related to the effect of energy on conformational changes in polymer chains. Herein, an isotactic polybutene-1 (iPB-1) crystal was crystallized from solution by adding a precipitant at various temperatures. The solution-crystallized iPB-1 crystal was heated to 100 °C to obtain form II at different heat rates and the transition of form II was characterized. It was found that the form II to form I transition was not only related to the precipitation temperature but also to the heating rate of the solution-crystallized iPB-1. Thus, both precipitation temperature and heating rate determine the formation temperature of form II, , form II that crystallized at lower temperature would transform faster. The results indicate that the conformation or conformational entropy of the amorphous region in iPB-1 is important to understand crystal transition.
溶液或熔体中的不同聚合物链在每个时刻都具有不同的构象以及相应的熵,而这些在结晶后会受到限制。基于平衡概念的构象或构象熵取决于链动力学,这与能量对聚合物链构象变化的影响有关。在此,通过在不同温度下添加沉淀剂,使全同立构聚丁烯-1(iPB-1)晶体从溶液中结晶。将溶液结晶的iPB-1晶体加热至100°C,以不同的加热速率获得晶型II,并对晶型II的转变进行了表征。发现晶型II向晶型I的转变不仅与沉淀温度有关,还与溶液结晶的iPB-1的加热速率有关。因此,沉淀温度和加热速率都决定了晶型II的形成温度,即在较低温度下结晶的晶型II转变速度更快。结果表明,iPB-1中非晶区的构象或构象熵对于理解晶体转变很重要。