Self-nucleation Effect of Crystallization with Various Nucleating Agents

In this work,the self-nucleation effect on crystallization was studied for polypropylene with various nucleating agents.The talc was employed to accelerate crystallization of monoclinic α-crystallites,while N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide TMB-5 was used to accelerate the crystallization kinetics and also induce formation of trigonal β-crystallites.To induce self-nucleation effect,the occurrence criterion was assessed by the transition temperatures from various domains and the available temperature width.More importantly,the resulting influences of self-nucleation effect were quantified by the change of crystallization kinetics and the potential polymorphism variation.It was found that the α-nucleating agents of talc broadened the temperature window for inducing Domain Ⅱ by elevating the transition temperature from Domain Ⅰ to Domain Ⅱ.Although β-nucleating agent(β-NA)of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide TMB-5 elevated cooling crystallization temperature obviously,the temperature window for Domain Ⅱ was narrowed.It should be emphasized that in presence of β-NA TMB-5,the self-nucleation effect enhances the crystallization of α-crystallite,which show the competition with β-NA TMB-5.At last,the ternary PP/talc/TMB-5 blend was prepared with the same amounts of α-NA talc and β-NA TMB-5 and it exhibits a similar self-nucleation effect of crystallization,indicating the dominant role of β-NA TMB-5.

Memory Effect of Crystallization in 1-Butene/α-olefin Copolymers

The macromolecular architecture is the crucial factor in determining the arrangement of the ordering structures,which,because of the multiscale feature,may exhibit distinct melting behaviors and induce the so-called memory effect to affect the following recrystallization.Until present,the correlation between the occurrence of memory effect and the intrinsic molecular structure is still far from the comprehensive understanding.In this work,four kinds of 1-butene/α-olefin random copolymers were designed and synthesized using the(pyridyl-amino)hafnium catalyst to introduce the different branches.The branch length was precisely controlled by the specific α-olefin comonomers,which include 1-hexene,1-decene,1-tetradecene,and 1-octadecene,while the branch density was tuned by the incorporation.As expected,the incorporation of α-olefin co-units to poly(1-butene)backbone decreases the non-isothermal crystallization kinetics and the degree of crystallinity.More interestingly,the resulting linear branch can induce the occurrence of memory effect and the threshold concentration of co-units(i.e.,branch density)decreases with increasing the branch length.Based on the results of these 1-butene/α-olefin copolymers with designable branches,a direct correlation with the occurrence of memory effect and the fraction of amorphous region was established,which quantitatively indicates the degree of local segregation of the crystallized poly(1-butene)sequences by theα-olefin co-units.