Both terminated functional isotactic polypropylene(iPP) and block copolymers containing iPP segment are desirable for commercial applications.This paper provides a convenient,highly-efficient method to prepare hydroxyl-terminated isotactic polypropylene(iPP-t-OH) and functional di-block copolymer containing the iPP segment through a combination of coordination polymerization and coupling reaction.The coordination polymerization was catalyzed by TiCl_44/MgCl_2/AlEt_3 catalyst system using ZnEt_2 as chain transfer agent.Further,the Zn-terminated iPP was oxidized and subsequently hydrolyzed to provide iPP-t-OH.Soxhlet extraction and ^(13)C NMR were used to calculate the isotacticity of iPP-t-OH.The degree of polymerization and the number of hydroxyl groups at the chain end of iPP-t-OH were measured by GPC and ~1H NMR.Despite the high molecular weight and heterogeneous reaction,iPP-t-OH is effectively linked with PEG-t-NCO to produce di-block copolymers.DSC analysis of the di-block copolymer shows an obvious decrease in T_m and T_c,which indicated that PEG was successfully linked to the terminal end of iPP.
Ya-Nan YePei-Yuan LiYong-Gang ShangguanZhi-Sheng FuQiang ZhengZhi-Qiang Fan
Impact polypropylene copolymer (IPC), named polypropylene catalloy, not only possesses excellent impact property, but also presents good rigidity. Its superior performances result from the complicated composition and microstructure. In the present article, recent progress in the studies on microstructure, morphology, crystallization and rheological behavior of IPC is summarized, and findings of the authors and their collaborators are reported. In general, IPC is divided into three components, i.e., ethylene-propylene random copolymer (EPR), a series of different segment lengths ethylene-propylene copolymer (EbP) and propylene homopolymer. The reasonable macromolecular structures of EbP and a multilayered core-shell model of dispersed phase structure in IPC were proposed, in which the dispersed phase consists of an outer EbP shell, an inner EPR layer and an EbP core. It is found that the annealing at melt-state may lead to an abnormal phase inversion, and the phase inversion disappears when temperature cools down to room temperature. The cause of phase inversion is ascribed to the existence of EbP component, which results in the stronger activity of the dispersed phase. The crystalline structure and morphologic results confirm the formation of β-iPP in IPC. Furthermore, it is found that the ethylene content in IPC and cooling rate of the samples have an important influence on the formation of β-iPP. Based on the crystallization kinetics analyzed by Lauritzen-Hoffman theory, crystallization behavior of different IPC samples is discussed and it is proposed that the dilution effect of ethylene propylene copolymer has a more remarkable influence on surface nucleation than on crystal growth. In addition, annealing at high temperature can result in the changes of chain structure for IPC, and this instability is ascribed to the oxidative degradation and crosslink reaction mainly in iPP component.
