宽线固体核磁共振氢谱（1H NMR）是一种研究半晶高分子相结构的经典方法.本文以半晶聚乙烯的宽线固体1H NMR谱为例，探讨了通过Gaussian/Sinc、Gaussian和Lorentzian函数组合对宽线固体1H NMR谱图进行拟合的方案，并根据半晶聚乙烯的相结构成分对拟合得到的各信号成分进行归属.并在此基础上探讨了各个相结构中分子链运动与信号线型的相关性，以及利用宽线固体1H NMR谱测量半晶高分子结晶度存在的困难.
吴金泽
,
辛家祥
,
付晓彬
,
姚叶锋
. 通过宽线固体核磁共振氢谱研究半晶高分子的相结构[J]. 波谱学杂志, 2019
, 36(1)
: 23
-33
.
DOI: 10.11938/cjmr20182648
Wide-line solid-state proton nuclear magnetic resonance (1H NMR) spectrometry is a classical technique to study the phase structures of semi-crystalline polymers. In this paper, the wide-line solid-state 1H NMR spectrum of semi-crystalline polyethylene was acquired, and fitted with the combination of Gaussian/Sinc, Gaussian and Lorentzian functions. The four signal components decomposed from the wide-line solid-state 1H NMR spectra were assigned to the crystallization phase, crystalline interface phase, amorphous interface phase and amorphous phase, respectively. The chain dynamics in different phase was also studied with the temperature-dependent wide-line solid-state 1H NMR method. The difficulties in determining the crystallinity of semi-crystalline polymers with wide-line solid-state 1H NMR were discussed.
[1] BASSETT D C. Principles of polymer morphology[M]. Cambridge University Press, 1981.
[2] HORⅡ F, KITAMARU R. Refined NMR analysis of the phase structure of solutioncrystallized linear polyethylene[J]. J Polym Sci Pol Phys, 1978, 16(2):265-270.
[3] KITAMARU R, HORⅡ F, MURAYAMA K. Phase structure of lamellar crystalline polyethylene by solid-state high-resolution carbon-13 NMR detection of the crystalline-amorphous interphase[J]. Macromolecules, 1986, 19(3):636-643.
[4] CHENG J, FONE M, REDDY V N, et al. Identification and quantitative analysis of the intermediate phase in a linear highdensity polyethylene[J]. J Polym Sci Pol Phys, 1994, 32(16):2683-2693.
[5] HASHIMOTO T, SHIBAYAMA M, KAWAI H. Domain-boundary structure of styrene-isoprene block copolymer films cast from solution. 4. molecular-weight dependence of Lamellar microdomains[J]. Macromolecules, 1980, 13(5):1237-1247.
[6] MCBRIERTY V J, DOUGLASS D C. Recent advances in the NMR of solid polymers[J]. J Polym Sci Macromol Rev, 1981, 16(1):295-366.
[7] EDDY W. H, PER E K, PEDERSEN B. Crystallinity of polyethylene derived from solid-state proton NMR free induction decay[J]. J Phys Chem B, 1998, 102(28):5444-5450.
[8] CHEN Y, YANG G, CHEN Q. Solid-state NMR study on the structure and mobility of the noncrystalline region of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)[J]. Polymer, 2002, 43(7):2095-2099.
[9] TANAKA H, NISHI T. Study of block copolymer interface by pulsed NMR[J]. J Chem Phys, 1985, 82(9):4326-4331.
[10] ABRAGAM A, HEBEL L C. The principles of nuclear magnetism[M]. Clarendon Press, 1961:56-58.
[11] LOOK D C, LOWE I J, NORTHBY J A. Nuclear magnetic resonance study of molecular motions in solid hydrogen sulfide[J]. J Chem Phys. 1966, 44(9):3441-3452.
[12] ENGELSBERG M, LOWE I J. Free-inducation-decay measurements and determination of moments in CaF2[J]. Phys Rev B, 1974, 10(3):822-832.
[13] KLÜVER W, RULAND W. NMR-studies of semicrystalline polymers using pulse techniques[M]. Steinkopff, 1978.
[14] BERGMANN K, SCHMIEDBERGER H. A rapid method for the NMR-measurement of two-phase polymers[J]. Colloid Polym Sci, 1980, 258(1):24-26.
[15] DADAYLI D, HARRIS R K, KENWRIGHT A M, et al. Solid-state 1H n.m.r. studies of polypropylene[J]. Polymer. 1994, 35(19):4083-4087.
[16] KRISTIANSEN P E, HANSEN E W, PEDERSEN B. Phase distribution in polyethylene versus temperature probed by solid-state proton NMR free induction decay[J]. Polymer, 2000, 41(1):311-321.
[17] PER E K, AND E W H, PEDERSEN B. Phase distribution during isothermal crystallization of polyethylene probed by solid-state proton NMR free induction decay[J]. J Phys Chem B, 1999, 103(18):3552-3558.
[18] JAEGER C, HEMMANN F. EASY:a simple tool for simultaneously removing background, deadtime and acoustic ringing in quantitative NMR spectroscopy——part I:basic principle and applications[J]. Solid State Nucl Magn Reson, 2014, 57-58(1):22-28.
[19] HUANG Z J, JIANG J, SHI L Y, et al. Dependences of confining size and interfacial curvature on the glass transition of polydimethylsiloxane in self-ssembled block copolymers[J]. Macromol Chem Phys, 2018, 219(3):1700518.
[20] TENG C, XUE G. Unjamming transition and cold flow of polymer chains[J]. Acta Polym Sin, 2011, 11(9):1001-1006.
[21] ZHU L L, WANG X L, GU Q, et al. Effects of residual surfactant on the glass transition behavior of polystyrene/gold nanocomposites[J]. Polymer, 2015, 77:14-20.
[22] XIAO T, YAO Y F. Local and collective chain motions in semi-crystalline polyethylene-a solid-state NMR approach[J]. Chinese J Magn Reson, 2015, 32(2):208-227.
[23] JIANG T T, FU X B, WU J Z, et al. Structure and dynamics in the polymer-ceramic interface of Li1.5Al0.5G1.5P3O12/polyether solid electrolyte:A solid state NMR study[J]. Chinese J Magn Reson, 2017, 34(4):429-438. 姜婷婷, 付晓彬, 吴金泽, 等. Li1.5Al0.5Ge1.5P3O12/高分子固体电解质表界面结构与分子运动的固体NMR研究[J]. 波谱学杂志, 2017, 34(4):429-438.
[24] UEHARA H, KOMOTO T, YAMANOBE T. Relationship between solid-state molecular motion and morphology for ultrahigh molecular weight polyethylene crystallized under different conditions[J]. Macromolecules. 2000, 33(13):4861-4870.
[25] RASTOGI S, YAO Y, RONCA S, et al. Unprecedented high-modulus high-strength tapes and films of ultrahigh molecular weight polyethylene via solvent-free route[J]. Macromolecules, 2011, 44(14):5558-5568.
[26] 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.
