title: Chain structure, aggregation state structure, and tensile behavior of segmented ethylene-propylene copolymers produced by an oscillating unbridged metallocene catalyst.
abstract: Segmented ethylene-propylene copolymers (SEPs) with different propylene contents were prepared by an unbridged metallocene bis(2,4,6-trimethylindenyl)zirconium dichloride [(2,4,6-Me3Ind)2ZrCl2] catalyst. Due to oscillation of the unbridged ligands in the catalyst, the SEPs are composed of segments with low propylene contents, alternated by the segments with high propylene contents. Such a chain structure was verified by (13)C NMR and successive self-nucleation and annealing (SSA). As the propylene/ethylene feed ratio during copolymerization increases, the comonomer contents in both segments are increased, leading to noncrystallizability of the high propylene segments and smaller crystallinity of the low propylene segments. Consequently, SEPs may be used as thermoplastic elastomers (TPEs). The aggregation state structures at nano- and micro-scales were characterized with small angle X-ray scattering, transmission electron microscopy and polarized optical microscopy, and compared with those of ethylene-octene multiblocky copolymers (OBCs) with similar crystallinity. It is found that SEPs form thinner lamellar crystals with a lower melting temperature due to shorter length and higher comonomer content of the low propylene segments. Moreover, the short length of the high propylene segments in SEPs results in an evidently thinner amorphous layer among the lamellar crystals, thus lots of amorphous phases are excluded out of the interlamellae. Accordingly, ill-developed spherulites or even bundle crystals are formed in SEPs, as compared with the well-developed spherulites in OBCs. SEPs exhibit the tensile property of typical TPEs with diffused yielding and large strain at break.
authors.forename: Zai-Zai
authors.initials: ZZ
authors.lastname: Tong
authors.affiliation: ‡State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
authors.forename: Yao
authors.initials: Y
authors.lastname: Huang
authors.forename: Jun-Ting
authors.initials: JT
authors.lastname: Xu
authors.forename: Zhi-Sheng
authors.initials: ZS
authors.lastname: Fu
authors.forename: Zhi-Qiang
authors.initials: ZQ
authors.lastname: Fan