Local and Collective Chain Motions in Semi-Crystalline Polyethylenes—A Solid-State NMR Approach

doi:10.11938/cjmr20150206

Abstract

Abstract:

Solid-state NMR offers a unique way to monitor the local and collective chain motions in semi-crystalline polymers. In this review paper, we will briefly survey recent results on the solid-state NMR study of chain motions in semi-crystalline polyethylenes (PEs). We will demonstrate that the state-of-the-art solid-state NMR now can provide very detailed knowledge about the local and collective chain motions in semi-crystalline PEs, which is of great relevance to our understanding of the mechanical behaviors of polyethylene in the microscopic level.

Key words: polyethylene, segmental motion, chain diffusion, solid-state NMR

CLC Number:

O482.53

XIAO Ting，YAO Ye-feng*. Local and Collective Chain Motions in Semi-Crystalline Polyethylenes—A Solid-State NMR Approach[J]. Chinese Journal of Magnetic Resonance, 2015, 32(2): 208-227.

References

[1] Sperling L H. Introduction to Physical Polymer Science (4th ed)[M]. New York: John Wiley & Sons, 1992.

[2] Stehling F C, Mandelkern L. The glass temperature of linear polyethylene[J]. Macromolecules, 1970, 3(2): 242－252.

[3] McBrierty V J, McDonald I R. Nuclear magnetic relaxation in linear and branched polyethylene[J]. Polymer, 1975, 16(2): 125－133.

[4] Strobl G. The Physics of Polymers (2nd ed)[M]. Berlin: Springer-Verlag, 1997.

[5] Boyd R H. Relaxation processes in crystalline polymers: molecular interpretation — a review[J]. Polymer, 1985, 26(8): 1 123－1 133.

[6] Boyd R H. Relaxation processes in crystalline polymers: experimental behaviour — a review[J]. Polymer, 1985, 26(3): 323－347.

[7] Mansfield M, Boyd R H. Molecular motions, the relaxation, and chain transport in polyethylene crystals[J]. J Polym Sci Pol Phys, 1978, 16(7): 1 227－1 252.

[8] Ward I M, Hadley D W. An introduction to the Mechanical Properties of Solid Polymers (2nd ed)[M]. London: John Wiley & Sons, 1993.

[9] Long Y, Shanks R A, Stachurski Z H. Kinetics of polymer crystallisation[J]. Prog Polym Sci, 1995, 20(4): 651－701.

[10] Lu J, Mirau P A, Tonelli A E. Chain conformations and dynamics of crystalline polymers as observed in their inclusion compounds by solid-state NMR[J]. Prog Polym Sci, 2002, 27(2): 357－401.

[11] Spiess H W. Deuteron NMR — a new tool for studying chain mobility and orientation in polymers[J]. Adv Polym Sci, 1985, 66: 23－58.

[12] Spiess H W. Structure and dynamics of solid polymers from 2D and 3D NMR[J]. Chem Rew, 1991, 91(7): 1 321－1 338.

[13] Schmidt-Rohr K, Spiess H W. Multidimensional Solid-State NMR and Polymers[M]. London: Academic Press, 1994.

[14] Spiess H W. Interplay of structure and dynamics in macromolecular and supramolecular systems[J]. Macromolecules, 2010, 43(13): 5 479－5 491.

[15] Levitt M H. Spin Dynamics: Basics of Nuclear Magnetic Resonance[M]. New York: John Wiley & Sons, 2001.

[16] Hansen M R, Graf R, Spiess H W. Solid-state NMR in macromolecular systems: insights on how molecular entities move[J]. Acc Chem Res, 2013, 46 (9): 1 996－2 007.

[17] Flory P. Principle of Polymer Chemistry[M]. New York: Cornell University Press, 1953.

[18] Mandelkern L. Crystallization in Polymers[M]. New York: McGraw-Hill, 1964.

[19] Mandelkern L. An Introduction to Macromolecules[M]. New York: Springer-Verlag, 1983.

[20] Robertson R E. Polymer Order and Polymer Density[J]. J Phys Chem, 1965, 69(5): 1 575－1 578.

[21] Schnell I, Spiess H W. High-resolution ¹H NMR spectroscopy in the solid state: very fast sample rotation and multiplequantum coherences[J]. J Magn Reson, 2001, 151(2): 153－227.

[22] Brown S P, Spiess H W. Advanced solid-state NMR methods for the elucidation of structure and dynamics of molecular, macromolecular, and supramolecular systems[J]. Chem Rev, 2001, 101(12): 4 125－4 156.

[23] Baker A M E, Windle A H. Evidence for a partially ordered component in polyethylene from wide-angle X-ray diffraction[J]. Polymer, 2001, 42(2): 667－680.

[24] Rastogi S, Terry A E. Morphological implications of the interphase bridging crystalline and amorphousregions in semi-crystalline polymers[J]. Adv Polym Sci, 2005, 180: 161－194.

[25] Balijepalli S, Rutledge G C. Molecular simulation of the intercrystalline phase of chain molecules[J]. J Chem Phys, 1998, 109(16): 6 523－6 526.

[26] Flory P J, Yoon D Y, Dill K A. The interphase in lamellar semicrystalline polymers[J]. Macromolecules, 1984, 17(4): 862－868.

[27] Gautam S, Balijepalli S, Rutledge G C. Molecular simulations of the interlamellar phase in polymers: effect of chain tilt[J]. Macromolecules, 2000, 33(24): 9 136－9 145.

[28] Axelson D E, Russell K E. Characterization of polymers by means of ¹³C NMR spectroscopy: (a) Morphology by solid-state NMR (b) End-group studies[J]. Prog Polym Sci, 1985, 11(3): 221－282.

[29] Kitamaru R, Horii F, Hyon S H. Proton magnetic resonance studies of the phase structure of bulk-crystallized linear polyethylene[J]. J Polym Sci Pol Phys, 1977, 15(5): 821－836.

[30] Mandelkern L, Alamo R G, Kennedy M A. The interphase thickness of linear polyethylene[J]. Macromolecules, 1990, 23(21): 4 721－4 723.

[31] Mowery D M, Harris D J, Schmidt-Rohr K. Characterization of a major fraction of disordered all-trans chains in cold-drawn high-density polyethylene by solid-state NMR[J]. Macromolecules, 2006, 39(8): 2 856－2 865.

[32] Uehara H, Yamanobe T, Komoto T. Relationship between solid-state molecular motion and morphology for ultrahigh molecular weight polyethylene crystallized under different conditions[J]. Macromolecules, 2000, 33(13): 4 861－4 870.

[33] Organ S J, Keller A. Solution crystallization of polyethylene at high temperatures[J]. J Mater Sci, 1985, 20(5): 1 571－1 585.

[34] Flory P J. On the morphology of the crystalline state in polymers[J]. J Am Chem Soc, 1962, 84(15): 2 857－2 867.

[35] Billmeyer F W. Textbook of Polymer Science (3rd ed)[M]. New York: Wiley, 1984.

[36] Earl W L, Vanderhart D L. Observations in solid polyethylenes by Carbon-13 nuclear magnetic resonance with magic angle sample spinning[J]. Macromolecules, 1979, 12: 762－767.

[37] Vanderhart D L. Influence of molecular packing on solid-state ¹³C chemical shifts: the n-alkanes[J]. J Magn Reson, 1981, 44(1): 117－125.

[38] Perez E, Vanderhart D L. Morphological partitioning of chain ends and methyl branches in melt-crystallized polyethylene by ¹³C NMR[J]. J Polym Sci Pol Phys, 1987, 25(8): 1 637－1 653.

[39] Yao Y F. Influence of spatial constraints in non-crystalline regions on the polymer dynamics in semi-crystalline polyethylene: a solid state NMR study[D]. German: Johannes Gutenberg-Universitaet Mainz, 2007.

[40] (a) Yao Y F, Graf R, Spiess H W, et al. Morphological differences in semicrystalline polymers: Implications for local dynamics and chain diffusion[J]. Phys Rev E, 2007, 76(6): 060801－060804; (b) Yao Y F, Graf R, Spiess H W, et al. Restricted segmental mobility can facilitate medium-range chain diffusion: A NMR study of morphological influence on chain dynamics of polyethylene[J]. Macromolecules, 2008, 41(7): 2 514－2 519.

[41] Spiess H W. Molecular dynamics of solid polymers as revealed by deuteron NMR[J]. Colloid Polym Sci, 1983, 261(3): 193－209.

[42] Yao Y F, Rastogi S, Xue H J, et al. Segmental mobility in the noncrystalline regions of nascent polyethylene synthesized using two different catalytic systems with implications on solid-state deformation[J]. Polymer, 2013, 54(1): 411－422.

[43] Yao Y, Jiang S, Rastogi S. 13C solid-state NMR characterization of structure and orientation development in the narrow and broad molar mass disentangled UHMWPE[J]. Macromolecules, 2014, 47(4): 1 371－1 382.

[44] VanderHart D L. Characterization of the methylene 13C chemical shift tensor in the normal alkane n-C20H42[J]. J Chem Phys, 1976, 64(2): 830－834.

[45] Schnell I. Dipolar recoupling in fast-MAS solid-state NMR spectroscopy[J]. Prog Nucl Mag Res Spectrosc, 2004, 45(1-2): 145－207.

[46] Saalwachter K, Schnell I. REDOR-based heteronuclear dipolar correlation experiments in multi-spin systems: rotor-encoding, directing, and multiple distance and angle determination[J]. Solid State Nucl Magn Reson, 2002, 22(2-3): 154－187.

[47] Davis G T, Eby R K. Glass transition of polyethylene: Volume relaxation[J]. J Appl Phys, 1973, 44(10): 4 274－4 281.

[48] Cho T Y, Shin E J, Jeong W, et al. Effects of comonomers on lamellar and noncrystalline microstructure of ethylene copolymers[J]. Macromol Rapid Commun, 2006, 27(5): 322－327.

[49] Demus D, Goodby J W, Gray G W, et al. Handbook of Liquid Crystals[M]. New York: Wiley-VCH, 1998.

[50] Liu S F, Mao J D, Schmidt-Rohr K. A robust technique for two-dimensional separation of undistorted chemical-shift anisotropy powder patterns in magic-angle-spinning NMR[J]. J Magn Reson, 2002, 155(1): 15－28.

[51] Axelson D E, Mandelkern L, Popli R, et al. 13C NMR of polyethylenes: Correlation of the crystalline component T₁ with structure[J]. J Polym Sci Pol Phys, 1983, 21(11): 2 319－2 335.

[52] Hu W G, Schmidt-Rohr K. Polymer ultradrawability: the crucial role of α-relaxation chain mobility in the crystallites[J]. Acta Polym, 1999, 50(8): 271－285.

[53] Hu W G, Boeffel C, Schmidt-Rohr K. Chain flips in polyethylene crystallites and fibers characterized by dipolar ¹³C NMR[J]. Macromolecules, 1999, 32(5): 1 611－1 619.

[54] Schnell I, Watts A, Spiess H W. Double-quantum double-quantum MAS exchange NMR spectroscopy: dipolar-coupled spin pairs as probes for slow molecular dynamics[J]. J Magn Reson, 2001, 149(1): 90－102.

[55] Schmidt-Rohr K, Spiess H W. Chain diffusion between crystalline and amorphous regions in polyethylene detected by 2D exchange carbon-13 NMR[J]. Macromolecules, 1991, 24(19): 5 288－5 293.

[56] Yao Y F, Graf R, Spiess H W, et al. Influence of crystal thickness and topological constraints on chain diffusion in linear polyethylene[J]. Macromol Rapid Commun, 2009, 30(13): 1 123－1 127.

[57] Torchia D A. The measurement of proton-enhanced carbon-13 T₁ values by a method which suppresses artifacts[J]. J Magn Reson, 1978, 30(3): 613－616.

[58] Doi M, Edwards S F. The Theory of Polymer Dynamics[M]. Oxford: Oxford University Press, 1986.

[59] Wei Y, Graf R, Sworen J C, et al. Local and Collective motions in precise polyolefins with alkyl branches: a combination of ²H and ¹³C solid-state NMR spectroscopy[J]. Angew Chem Int Edit, 2009, 48(25): 4 617－4 620.

[60] Lieser G, Wegner G, Smith J A, et al. Morphology and packing behavior of model ethylene/propylene copolymers with

precise methyl branch placement[J]. Colloid Polym Sci, 2004, 282(8): 773－381.