通过宽线固体核磁共振氢谱研究半晶高分子的相结构
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摘要
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.
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.
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.
引文
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[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.
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[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:Asolid 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.
[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 NMRdetection 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 NMRspectroscopy--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:Asolid 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.