Chinese Journal of Magnetic Resonance >
Dynamic Evolution in PVPh/PEO Blend Studied by Solid-State NMR
Received date: 2015-12-30
Revised date: 2016-04-09
Online published: 2016-06-05
The 13C centerband-only-detection-of-exchange (CODEX) variable-temperature solid-state NMR (SSNMR) technique was used to investigate the evolution of segmental dynamics in poly (vinyl phenol) (PVPh)/poly (ethylene oxide) (PEO) polymer blend within a wide range of temperatures. It was found that the glass transition began with the emergence of remarkable slow motions of the PVPh backbone segments, and ended when the CODEX signal intensity of segmental slow motion reached maximum. The SSNMR results revealed, at molecular level, that the onset and endpoint of conventional calorimetric glass transition are closely associated with the evolution of slow motions in this polymer blend.
Key words： solid-state NMR(SSNMR); polymer blend; dynamics; slow motion
LI Bao-hui , PENG Yong-jin , SUN Ping-chuan . Dynamic Evolution in PVPh/PEO Blend Studied by Solid-State NMR[J]. Chinese Journal of Magnetic Resonance, 2016 , 33(2) : 188 -197 . DOI: 10.11938/cjmr20160202
[1] Dong Jian-hua(董建华). The Frontier and Progress of Polymer Science(高分子科学前沿与进展)[M]. Beijing(北京):Science Press(科学出版社), 2006.
[2] Paul D, Bucknall C. Polymer Blends[M]. New York:John Wiley & Sons Inc. 2000.
[3] Shi P, Schach R, Munch E, et al. Glass transition distribution in miscible polymer blends:From calorimetry to rheology[J]. Macromolecules, 2013, 46(9):3611-3620.
[4] Evans C M, Torkelson J M. Determining multiple component glass transition temperatures in miscible polymer blends:Comparison of fluorescence spectroscopy and differential scanning calorimetry[J]. Polymer, 2012, 53(26):6118-6124.
[5] Wachowicz M, Gill L, Wolak J, et al. Polypropylene and polyethylene-copolymer blend miscibility:Slow chain dynamics in individual blend components near the glass transition[J]. Macromolecules, 2008, 41(8):2832-2838.
[6] Wachowicz M, Gill L, White J L. Polyolefin blend miscibility:Polarization transfer versus direct excitation exchange nmr[J]. Macromolecules, 2008, 42(2):553-555.
[7] Wachowicz M, White J L. Miscible blend dynamics and thermodynamics:Quantitatively untangling slow conformational events in amorphous polymer mixtures[J]. Macromolecules, 2007, 40(15):5433-5440.
[8] Colmenero J, Arbe A. Segmental dynamics in miscible polymer blends:Recent results and open questions[J]. Soft Matter, 2007, 3(12):1474-1485.
[9] Lodge T P, McLeish T C B. Self-concentrations and effective glass transition temperatures in polymer blends[J]. Macromolecules, 2000, 33(14):5278-5284.
[10] Schantz S. Structure and mobility in poly (ethylene oxide)/poly (methyl methacrylate) blends investigated by 13C solid-state NMR[J]. Macromolecules, 1997, 30(5):1419-1425.
[11] Schmidt-Rohr K, Spiess H W. Multidimensional Solid-State NMR and Polymers[M]. London:Academic Press, 1994.
[12] Levitt M H. Spin Dynamics:Basics of Nuclear Magnetic Resonance[M]. Chichester:John Wiley & Sons Inc. 2001.
[13] Hansen M R, Graf R, Spiess H W. Solid-state NMR in macromolecular systems:Insights on how molecular entities move[J]. Accounts Chem Res, 2013, 46(9):1996-2007.
[14] de Azevedo E R, Hu W G, Bonagamba T J, et al. Principles of centerband-only detection of exchange in solid-state nuclear magnetic resonance, and extension to four-time centerband-only detection of exchange[J]. J Chem Phys, 2000, 112(20):8988-9001.
[15] Schmidt-Rohr K, de Azevedo E R, Bonagamba T J. Centerband-Only Detection of Exchange (Codex):Efficient NMR Analysis of Slow Motions in Solids[M]. Doi:10.1002/9780470034590.
[16] Gill L, Damron J, Wachowicz M, et al. Glass transitions, segmental dynamics, and friction coefficients for individual polymers in multicomponent polymer systems by chain-level experiments[J]. Macromolecules, 2010, 43(8):3903-3910.
[17] Zhang X, Takegoshi K, Hikichi K. Composition dependence of the miscibility and phase structure of amorphous/crystalline polymer blends as studied by high-resolution solid-state carbon-13 NMR spectroscopy[J]. Macromolecules, 1992, 25(9):2336-2340.
[18] Rinderknecht S, Brisson J. Orientation of a miscible polymer blend with strong interchain hydrogen bonds:Poly (vinylphenol)-poly (ethylene oxide)[J]. Macromolecules, 1999, 32(25):8509-8516.
[19] Zhang R C, Chen T H, Sun P C, et al. Investigation on the artificial exchange signals induced by the rider effect in codex experiments[J]. Solid State Nucl Mag, 2012, 47-48(4):28-34.
[20] de Azevedo E, Hu W G, Bonagamba T, et al. Centerband-only detection of exchange:Efficient analysis of dynamics in solids by NMR[J]. J Am Chem Soc, 1999, 121(36):8411-8412.
[21] Moskala E J, Varnell D F, Coleman M M. Concerning the miscibility of poly (vinyl phenol) blends FT i.r. study[J]. Polymer, 1985, 26(2):228-234.
[22] Qin C, Pires T N, Belfiore L A. Morphological and physicochemical interactions in semicrystalline polymer-polymer blends[J]. Polymer Communications, 1990, 31(5):177-182.
[23] Bloise A C, de Azevedo R F, Cossiello R F, et al. Solid-state nuclear magnetic resonance study of relaxation processes in MEH-PPV[J]. Phys Rev B, 2005, 71(17):174-202.
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