The Crystal-Crystal Transition in Hydrogenated Ring-Opened Polynorbornenes: Tacticity, Crystal Thickening, and Alignment

被引:20
作者
Bishop, John P. [1 ]
Register, Richard A. [1 ]
机构
[1] Princeton Univ, Dept Chem Engn, Princeton, NJ 08544 USA
基金
美国国家科学基金会;
关键词
crystal structures; hydrogenation; polymorphism; polynorbornene; ROMP; OPENING METATHESIS POLYMERIZATION; ALKYLIDENE COMPLEXES; MORPHOLOGY; PHASE; CRYSTALLIZATION; NORBORNADIENES; POLYETHYLENE; POLYMERS; ORIENTATION; NORBORNENES;
D O I
10.1002/polb.22124
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
At a temperature T-cc well below its melting point T-m, hydrogenated ring-opened polynorbornene (hPN) is known to exhibit a crystal-crystal transition; above T-cc, the hPN chains are rotationally disordered. This transition is examined in a series of hPNs polymerized with different Mo- and Ru-based catalysts, each of which imparts a slightly different tacticity to the polymer. T-cc is found to correlate well with the ratio of meso to racemo dyads (m:r); small changes in m: r (from 0.8 to 1.1) are sufficient to raise T-cc by nearly 20 degrees C. For the homogeneous Mo-based "Schrock-type" catalyst examined, such a change in m:r is easily achieved by simply adding the reversibly binding ligand trimethylphosphine during polymerization. T-cc approaches T-m with increasing m:r, indicating that r dyads stabilize the rotationally disordered structure. When heated above T-cc, hPN crystals thicken at a rate much greater than conventional three-dimensionally ordered crystals, but below the rates shown by the two-dimensional hexagonal (columnar) phase formed by some polymers, reflecting the intermediate level of order and chain mobility present in the high-temperature hPN crystal phase. Solid-state processing of hPN between T-cc and T-m yields highly aligned macroscopic specimens. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 68-79, 2011
引用
收藏
页码:68 / 79
页数:12
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