原位液体核磁共振在高分子材料表征领域的应用

doi:10.11938/cjmr20182701

摘要/Abstract

摘要： 随着原位系统研究的进步以及灵敏度的提高，原位核磁共振在高分子材料领域的应用越来越广泛.原位液体核磁共振具有分析速度快、适用范围宽、无损检测、无需标样等特点，多用于表征聚合反应动力学及反应机理.除此之外，它还可以通过与其他仪器进行联用、匹配适用的探头等手段分离并解析未知物的化学结构.因此，原位液体核磁共振波谱技术将成为高分子科学研究领域不可或缺的通用工具.

关键词: 原位液体核磁共振, 反应动力学, 可逆加成断裂链转移聚合, 表征方法联用

Abstract: With the shift toward the study of systems in operando and with increasing sensitivity, in operando nuclear magnetic resonance (NMR) is becoming more and more widely used in the field of polymer materials. In operando liquid state NMR provide mechanistic and kinetic information on polymerization reactions with the needless for stable labeling isotope, fast analysis, wide application range and maintaining intact samples. In addition, using the hyphenation of other characterization methods with in operando NMR spectroscopy is one of the most powerful methods for the separation and structural elucidation of unknown compounds and molecular compositions of mixtures by designing a suitable probe. In operando NMR spectroscopy will remain an indispensable and versatility tool in macromolecular science for years to come.

Key words: in operando liquid state NMR, reaction kinetics, reversible addition-fragmentation transfer polymerization, hyphenation characterization methods

中图分类号:

O482.53

万至彬, 宋建会, 郭鸣明. 原位液体核磁共振在高分子材料表征领域的应用[J]. 波谱学杂志, 2019, 36(3): 408-424.

WAN Zhi-bin, SONG Jian-hui, GUO Ming-ming. The Application of in Operando Liquid State NMR on Macromolecular Material Characterization[J]. Chinese Journal of Magnetic Resonance, 2019, 36(3): 408-424.

参考文献

[1] RABI I I, ZACHRIAS J R, MILLMAN S, et al. A new method of measuring nuclear magnetic moment[J]. Phys Rev, 1938, 53(4):318.
[2] THE NOBEL FOUNDATION. Nobel lectures including presentation speeches and laureates' biographies-physics 1942-1962[M]. Amsterdam:Elsevier Publishing Company, 2013:20.
[3] ERNST R R, ANDERSON W A. Application of Fourier transform spectroscopy to magnetic resonance[J]. Rev Sci Instrum, 1966, 37(1):93-102.
[4] 王虎. 光引发活性自由基聚合反应的原位核磁跟踪研究[D]. 合肥:中国科学技术大学, 2013.
[5] AlAM T M, ALAM M K. Chemometric analysis of NMR spectroscopy data:A review[J]. Annual Reports on NNR Spectroscopy, 2004, 54:41-80.
[6] CONSONN R, CAGLIANI L R. Geographical characterization of polyfloral and acacia honeys by nuclear magnetic resonance and chemometrics[J]. J Agri Food Chem, 2008, 56(16):6873-6880.
[7] DENG F, XIAO L Z, TAO Y, et al. Low-field and on-line NMR detection for fluid molecular structure[J]. Chinese J Magn Reson, 2017, 34(2):91-99.邓峰, 肖立志, 陶冶, 等. 低场核磁共振流体分子结构在线探测技术[J]. 波谱学杂志, 2017, 34(2):91-99.
[8] UEKI R, YAMAGUCHI K, NONAKA H, et al. H-1 NMR probe for in situ monitoring of dopamine metabolism and its application to inhibitor screening[J]. J Am Chem Soc, 2012, 134(30):12398-12401.
[9] HAW J F. In-situ spectroscopy in heterogeneous catalysis[M]. Wiley-VCH Verlag GmbH & Co. KGaA, 2004.
[10] EMSLEY L. Advances in magnetic resonance:from stem cells to catalytic surfaces[J]. J Am Chem Soc, 2013, 135(22):8089-8091.
[11] 张正行. 有机光谱分析[M]. 北京:人民卫生出版社, 2009.
[12] 陈厚. 高分子材料分析测试与研究方法[M]. 北京:化学工业出版社, 2011.
[13] FENG Y X, CHU X L, XU Y P, et al. Process nuclear magnetic resonace technology and its applications[J]. Modern Scientific Instruments, 2013(6):109-109.冯云霞, 褚小立, 许育鹏, 等. 在线核磁共振过程分析技术及其应用[J]. 现代科学仪器, 2013(6):109-109.
[14] 宁永成. 有机波谱学谱图解析[M]. 北京:科学出版社, 2010.
[15] NAJAFI V, ZIAEE F, KABIRI K, et al. Aqueous free-radical polymerization of PEGMEMA macromer:kinetic studies via an on-line H NMR technique[J]. Iran Polym J, 2012, 21(10):683-688.
[16] HEROLD H, HARDY E H, RANFT M. et al. Online Rheo-TD NMR for analysing batch polymerisation processes[J]. Micropor Mesopor Mat, 2013, 178(13):74-78.
[17] 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.
[18] WALTER E D, QI L, CHAMAS A, et al. Operando MAS NMR reaction studies at high temperatures and pressures[J]. J Phys Chem C, 2018, 122(15):8209-8215.
[19] ZHANG X Q, PAN Y J, LI Y. The application of NMR on hign molecular polymers[J]. Modern Scientific Instruments, 2001(6):29-33.张雪芹, 潘远江, 李杨. 核磁共振方法在高分子聚合物方面的应用[J]. 现代科学仪器, 2001(6):29-33.
[20] SCHNELL I, LANGER B, SONTJENS S H M, et al. Quadruple hydrogen bonds of ureido-pyrimidinone moieties investigated in the solid state by ¹H double-quantum MAS NMR spectroscopy[J]. Phys Chem Chem Phys, 2002, 4:3750-3758.
[21] LI S, ZHENG J P, GUO M M. In situ variable-temperature multi-nuclear NMR studies of the thermal decomposition mechanism of ionic liquid[J]. Chinese J Magn Reson, 2017, 34(2):156-163.李森, 郑俊鹏, 郭鸣明. 离子液体热分解机理的原位变温多核核磁共振研究[J]. 波谱学杂志, 2017, 34(2):156-163.
[22] ZAHEER M A, ZILL J C, MATYSIK J, et al. In situ and in operando characterization of mixing dynamics in liquid-phase reactions by ¹²⁹Xe NMR spectroscopy[J]. Chemphyschem, 2017, 18(12):1513-1516.
[23] STEINRUCK H P, WASSERSCHEID P. Ionic liquids in catalysis[J]. Catal Lett, 2015, 145(1):380-397.
[24] PERA-TITUS M, LECLERCG L, CLACENS J M, et al. Pickering interfacial catalysis for biphasic systems:from emulsion design to green reactions[J]. Angew Chem Int Ed, 2015, 54(7):2006-2021.
[25] ZHU Y C, LIU B, XU D Y, et al. Application of nuclear magnetic resonance and its combined technology in qualitative and quantitative analysis of natural products[J]. Modern Pharmmacy and Clinic, 2009, 24(4):193-197. 朱颖超, 刘斌, 徐冬艳, 等. 核磁共振及其联用技术在天然产物定性定量分析中的应用[J]. 现代药物与临床, 2009, 24(4):193-197.
[26] YUAN L, LIU K, BEI F L, et al. Formation mechanism of flower-like nanostructured polyaniline prepared under guidance of L-valine[J]. Acta Polymerica Sinica, 2017, 49(4):605-615.袁丽, 刘空, 卑凤利, 等. 原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究[J]. 高分子学报, 2017, 49(4):605-615.
[27] WANG R R, WANG C S, LIU K, et al. Nucleation of polyaniline nano-/macrotubes from anilinium composed micelles[J]. J Phys Chem B, 2014, 118(9):2544-2552.
[28] YANG W M, WANG H Q, YAN X Z, et al. NMR study on reaction kinetics of ring-opening polymerization of propylene oxide (PO)[J]. Acta Polymerica Sinica, 1993(4):456-462.杨薇蔓, 汪汉卿, 颜星中, 等. 原位核磁研究环氧丙烷的开环聚合反应动力学[J]. 高分子学报, 19931(4):456-462.
[29] MAIWALD M, FISCHER H H, KIM Y K, et al. Quantitative high-resolution on-line NMR spectroscopy in reaction and process monitoring[J]. J Magn Reason, 2004, 166(2):135-146.
[30] VARGAS M A, CUDAJ M, HAILU K, et al. Online low-field ¹H NMR spectroscopy:monitoring of emulsion polymerization of butyl acrylate[J]. Macromolecules, 2010, 43(13):5561-5568.
[31] QIU K Y. Progress of free radical polymerization in recent years[J]. Polymer Bulletin, 2008(7):15-28.丘坤元. 自由基聚合近20年的发展[J]. 高分子通报, 2008(7):15-28.
[32] ZHENG A N, GUAN Y, WEI D F, et al. Current situation and breakthrough efforts of the anionic polymerization of olefins after the development for 60 years[J]. Journal of Founctional Polymers, 2017(4):367-421.郑安呐, 管涌, 危大福, 等. 烯烃阴离子聚合发展60年的现状与释疑的努力[J]. 功能高分子学报, 2017(4):367-421.
[33] JENKINS A D, JONES R G, MOAD G. Terminology for reversible-deactivation radical polymerization previously called "controlled" radical or "living" radical polymerization (IUPAC Terminology 2010)[J]. Pure Appl Chem, 2010, 82:483-491.
[34] CHIEFARI J, CHONG Y K, ERCOLE F, et al. Living free-radical polymerization by reversible addition-fragmentation chain transfer:The RAFT process[J]. Macromolecules, 1998, 31(16):5559-5562.
[35] GRUBBS R B, GRUBBS R H. 50th anniversary perspective:living polymerization-emphasizing the molecule in macromolecules[J]. Macromolecules, 2017, 50(18):6979-6997.
[36] WEI X L, WEI YL, GONG G B, et al. Applications of controlled radcial polymerization technology in polymer materials synthesis[J]. China Synthetic Rubber Industry, 2016, 39(4):338-344.魏绪玲, 魏玉玲, 龚光碧, 等. 可控自由基聚合技术在合成高分子材料中的应用[J]. 合成橡胶工业, 2016, 39(4):338-344.
[37] PERRIER S. 50th anniversary perspective:raft polymerization-a user guide[J]. Macromolecules, 2017, 50(19):7433-7447.
[38] VANA P, QUINN J F, DAVIS T P, et al. Recent advances in the kinetics of reversible addition fragmentation chain-transfer polymerization[J]. Aust J Chem, 2002, 55(7):425-431.
[39] MCLEARY J B, CALITZ F M, MCKENZIE J M, et al. Beyond inhibition: A ¹H NMR investigation of the early kinetics of RAFT-mediated polymerization with the same initiating and leaving groups[J]. Macromolecules, 2004, 37(7):2383-2394.
[40] CALITZ F M, MCLEARY J B, MCKENZIE J M, et al. Evidence for termination of intermediate radical species in raft-mediated polymerization[J]. Macromolecules, 2003, 36(26):9687-9690.
[41] ZHENG G H, PAN C Y. Reversible addition-fragmentation transfer polymerization in nanosized micelles formed in situ[J]. Macromolecules, 2006, 39(1):95-102.
[42] KEDDIE D J. A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization[J]. Chem Soc Rev, 2014, 43(2):496-505.
[43] CHEN S A, CHANG G Y. Kinetics of the copolymerization of styrene with maleic anhydride in ethyl methyl ketone[J]. Macromol Chem Phys, 1986, 187(7):1597-1602.
[44] SANAYEI R A, O'DRISCOLL K F, KLUMPERMAN B. Pulsed laser copolymerization of styrene and maleic anhydride[J]. Macromolecules, 1994, 27(20):5577-5582.
[45] DU F S, ZHU M Q, GUO H Q, et al. An ESR study of reversible addition-fragmentation chain transfer copolymerization of styrene and maleic anhydride[J]. Macromolecules, 2002, 35(17):6739-6741.
[46] ZHU M Q, WEI L H, LI M, et al. A unique synthesis of a well-defined block copolymer having alternating segments constituted by maleic anhydride and styrene and the self-assembly aggregating behavior thereof[J]. Chem Commun, 2001, 4(4):365-366.
[47] VAN DEN DUNGEN E T A, RINQUEST J, PRETORIUS N O, et al. Investigation into the initialization behavior of RAFT-mediated styrene-maleic anhydride copolymerizations[J]. Aust J Chem, 2007, 38(6):742-748.
[48] LIU N, GUO M M. Application of in situ in research of RAFT-mediated styrene-maleic anhydride copolymerization[J]. China Synthetic Resin and Plastics, 2018, 35(1):1-5刘娜, 郭鸣明. 用原位核磁研究苯乙烯与马来酸酐的RAFT共聚合[J]. 合成树脂及塑料, 2018, 35(1):1-5.
[49] 郭鸣明.原位核磁共振及DOSY研究室温附近RAFT聚合水溶性高分子4-Acryloylmorpholine(AML)及其嵌段共聚物AML-b-AA-b-AML[C]//中国物理学会波谱专业委员会, 第十八届全国波谱学学术年会论文集. 2014.
[50] LI W, HUANG K, DONG Y Y, et al. Influence study of pyrolysis kinetics and volatile product characteristics of eucalyptus on slagging based on Tg-DTg-FTIR technique[J]. Acta Energiae Solaris Sinica, 2016, 37(12):3233-3239.李薇, 黄奎, 董艳艳, 等. 热重-红外联用技术分析桉树热解动力学及挥发产物对结渣影响研究[J]. 太阳能学报, 2016, 37(12):3233-3239.
[51] WANG D L, WANG H J, WANG L N, et al. Analysis and comparison of polycyclic aromatic hydrocarbons by gas chromatography-mass spectrometry and high performance liquid chromatography[J]. Henan Chemical Industry, 2018(5):53-55.王大陆, 汪宏杰, 王丽娜, 等. 气相色谱-质谱联用和高效液相色谱法对多环芳烃的分析及对比[J]. 河南化工, 2018(5):53-55.
[52] YU H. The investigation of NMR determination for isotactic index of homopolypropylene[J]. Petrochemcial Industry Technology, 2011, 18(4):17-19.于红. 核磁共振法测定均聚聚丙烯等规指数[J]. 石化技术, 2011, 18(4):17-19.
[53] ALBERT K. On-line use of NMR detection in separation chemistry[J]. J Chromatogr A, 1995, 703(1,2):123-147.
[54] ALBERT K, DACHTLER M, GLASER T, et al. On-line coupling of separation techniques to NMR[J]. J Sep Sci, 2015. 22(3):135-143.
[55] HILLER W, SINHA P, PASCH H. Online HPLC-NMR of PS-b-PMMA and blends of PS and PMMA, 2-LCCC-NMR at critical conditions of PS[J]. Macromolecular Chemistry & Physics, 2010, 208(18):1965-1978.
[56] HILLER W, SINHA P, PASCH H. Online HPLC-NMR of PS-b-PMMA and blends of PS and PMMA, 2-LCCC-NMR at critical conditions of PMMA[J]. Macromolecular Chemistry & Physics, 2010, 210(8):605-613.
[57] HILLER W, HEHN M, HOFE T, et al. Online size exclusion chromatography-NMR for the determination of molar mass distributions of copolymers[J]. Anal Chem, 2010, 82(19):8244-8250.
[58] HSIEH H L. Anionic polymerization-principles and practical applications[J]. Biomedical Applications of Electroactive Polymers, 1996, 44(6):591-621.
[59] HILLER W, HEHN M, SINHA P, et al. Online coupling of two-dimensional liquid chromatography and NMR for the analysis of complex polymers[J]. Macromolecules, 2012, 45(19):7740-7748.
[60] ALBERT K, BRAUMANN U, STRECK R, et al. Application of direct on-line coupling of HPLC and SFC with ¹H NMR spectroscopy for the investigation of monomeric acrylates[J]. Fresen J Anal Chem, 1995, 352(5):521-528
[61] SCHLOTTERBECK G, TSENG LH, HÄNDEL H, et al. Direct on-line coupling of capillary HPLC with ¹H NMR spectroscopy for the structural determination of retinyl acetate dimers:2D NMR spectroscopy in the nanoliter scale[J]. Anal Chem, 1997, 69(7):1421-1425.
[62] HILLER W, PASCH H, MACKO T, et al. On-line coupling of high temperature GPC and ¹H NMR for the analysis of polymers[J]. J Magn Reson, 2006, 183(2):290-302.
[63] CAO S H, NI Z R, HUANG L, et al. In situ monitoring potential-dependent electrochemical process by liquid NMR spectroelectrochemical determination:a proof-of-concept study[J]. Anal Chem, 2017, 89(7):3810-3813.
[64] BUSSY U, GIRAUDEAU P, SILVESTRE V, et al. -In situ NMR spectroelectrochemistry for the structure elucidation of unstable intermediate metabolites[J]. Anal Bioanal Chem, 2013, 405(17):5817-5824.
[65] BEWERIES T, FISCHER C, PEITZ S, et al. Combination of spectroscopic methods:in situ NMR and UV/Vis measurements to understand the formation of group 4 metallacyclopentanes from the corresponding metallacyclopropenes[J]. J Am Chem Soc, 2009, 131(12):4463-4469.
[66] FAVIERA, BARNER-KOWOLLIK C, DAVIS T P, et al. A detailed on-line FT/NIR and ¹H NMR spectroscopic investigation into factors causing inhibition in xanthate-mediated vinyl acetate polymerization[J]. Macromolecular Chemistry & Physics, 2010, 205(7):925-936.
[67] ODIAN G. Principles of polymerization[M]. Fourth Edition. America:Wiley-Interscience, 2004.
[68] SCHILLI C, LANZENDÖRFER M G, MÜLLER A H E. Benzyl and cumyl dithiocarbamates as chain transfer agents in the RAFT polymerization of N-isopropylacrylamide. In situ FT-NIR and MALDI-TOF MS investigation[J]. Macromolecules, 2002, 35(18):6819-6827.