The Effect of NMR Setting Parameters on Molecular Weight Determination of Polyether Diols

Shu-Jie Huang; Xiao-Hong Li; Ying-Feng Tu

doi:10.1007/s10118-024-3172-y

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The Effect of NMR Setting Parameters on Molecular Weight Determination of Polyether Diols

RESEARCH ARTICLE | Updated：2024-11-04

- The Effect of NMR Setting Parameters on Molecular Weight Determination of Polyether Diols
- The Effect of NMR Setting Parameters on Molecular Weight Determination of Polyether Diols
- 高分子科学（英文版） 2024年42卷第11期页码：1730-1737
- Affiliations：
  
  Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
- Author bio：
  
  lxh83@suda.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 22231008 and 22071167), the Natural Science Foundation of Jiangsu Higher Education Institutions of China (No. 22KJA150005) and a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-024-3172-y.
- DOI：10.1007/s10118-024-3172-y
  中图分类号：
- 收稿：2024-04-16，
  
  修回：2024-05-12，
  
  录用：2024-05-22，
  
  网络首发：2024-08-20，
  
  纸质出版：2024-11-30
- Accepted：
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Huang, S. J.; Li, X. H.; Tu, Y. F. The effect of NMR setting parameters on molecular weight determination of polyether diols. Chinese J. Polym. Sci. 2024, 42, 1730–1737

Shu-Jie Huang, Xiao-Hong Li, Ying-Feng Tu. The Effect of NMR Setting Parameters on Molecular Weight Determination of Polyether Diols[J]. Chinese Journal of Polymer Science, 2024, 42(11): 1730-1737.
Huang, S. J.; Li, X. H.; Tu, Y. F. The effect of NMR setting parameters on molecular weight determination of polyether diols. Chinese J. Polym. Sci. 2024, 42, 1730–1737 DOI： 10.1007/s10118-024-3172-y.

Shu-Jie Huang, Xiao-Hong Li, Ying-Feng Tu. The Effect of NMR Setting Parameters on Molecular Weight Determination of Polyether Diols[J]. Chinese Journal of Polymer Science, 2024, 42(11): 1730-1737. DOI： 10.1007/s10118-024-3172-y.

摘要

We investigate the effect of liquid

H NMR setting parameters on the MW determination of polyether diols

and the optimal quantitative NMR conditions are suggested as following: 90 degree of flip angle with inverted gated

C decoupling and 30 s

Abstract

Nuclear magnetic resonance (NMR) is an advanced technique for the molecular weight (MW) determination of polymers at quantitative conditions. In this study

we investigate the effect of liquid

H-NMR instrumental setting parameters on the MW determination of polyether diols

namely poly(ethylene glycol) (PEG) and poly(tetramethylene oxide) (PTMO) diols

using hydroxymethylene groups as chain-ends. Our results show that the protons in chain-ends have larger spin-lattice relaxation time (

) than those in main chains. To let most of the excited protons relax to the equilibrium state

the delay time (

) should be much larger than

of end-groups. When

C decoupling is inactive

the relative errors can be greater than 60%

due to the

C-coupled proton satellite peaks

which can overlap with chain-end groups or be misassigned as chain-ends. The optimal quantitative NMR conditions for the MW estimation of polyethers are revealed below: standard pulse with inverted gated

C decoupling pulse sequence

32 scans

2.0 s acquisition time in 90 degree of flip angle and 30 s

. The MWs determined from

H quantitati

ve NMR are all smaller than those from SEC which are relative to polystyrene (PS) standards

since the size of polyether chains is larger than that of PS with the same MW. In addition

the MW obtained from SEC for PTMOs shows larger overestimation than PEGs

suggesting PEG chains are more flexible than PTMO’s.

关键词

Keywords

references

Klein, R.; Wurm, F. R. Aliphatic polyethers: classical polymers for the 21 st century. Macromol. Rapid Commun. 2015 , 36 , 1147−1165..

Klinedinst, D. B.; Yilgör, I.; Yilgör, E.; Zhang, M.; Wilkes, G. L. The effect of varying soft and hard segment length on the structure–property relationships of segmented polyurethanes based on a linear symmetric diisocyanate, 1,4-butanediol and PTMO soft segments. Polymer 2012 , 53 , 5358−5366..

Wang, C.; Zolotarskaya, O.; Ashraf, K. M.; Wen, X.; Ohman, D. E.; Wynne, K. J. Surface characterization, antimicrobial effectiveness, and human cell response for a biomedical grade polyurethane blended with a mixed soft block PTMO-quat/PEG copolyoxetane polyurethane. ACS Appl. Mater. Interfaces 2019 , 11 , 20699−20714..

Seshimo, K.; Sakai, H.; Watabe, T.; Aoki, D.; Sugita, H.; Mikami, K.; Otsuka, H. Segmented polyurethane elastomers with mechanochromic and self-strengthening functions. Angew. Chem. Int. Ed. 2021 , 60 , 8406−8409..

Lee, J. S.; Taghavimehr, M.; Montazami, R.; Green, M. D. Synthesis and characterization of poly(ethylene glycol)-based segmented ionenes block copolymer with aliphatic or DABCO hard segments. Polymer 2022 , 242 , 124543..

Li, Z.; Shen, L.; Ma, A.; Talkington, A.; Li, Z.; Nyborg, A. C.; Lai, S. K. Pegloticase co-administered with high MW polyethylene glycol effectively reduces PEG-immunogenicity and restores prolonged circulation in mouse. Acta Biomater. 2023 , 170 , 250−259..

Paszkiewicz, S.; Walkowiak, K.; Irska, I.; Zubkiewicz, A.; Figiel, P.; Gorący, K.; El Fray, M. Furan-based copoly (ester-ethers) and copoly (ester-amide-ethers). Comparison study on the phase structure, mechanical and thermal properties. Polymer 2023 , 269 , 125740..

Li, C.; Zhang, J. N.; Jin, J.; Jiang, W. The effect of topologies and refilling short-chain PEG on protein adsorption. Chinese J. Polym. Sci. 2023 , 41 , 1879−1888..

Kim, B.; Lee, J.; Lee, E.; Jeong, K.; Seo, J. H. One-pot coatable fluorinated polyurethane resin solution for robust superhydrophobic anti-fouling surface. Prog. Org. Coat. 2024 , 187 , 108097..

Leroux, C. R.; McCormack, P. M.; Elango, S.; Geise, G. M.; Koenig Jr, G. M. Transport properties of ethylene glycol functionalized membranes exposed to nonaqueous electrolytes. Polymer 2024 , 300 , 126986..

Vrijsen, J. H.; Thomlinson, I. A.; Levere, M. E.; Lyall, C. L.; Davidson, M. G.; Hintermair, U.; Junkers, T. Online tracing of molecular weight evolution during radical polymerization via high-resolution flow NMR spectroscopy. Polym. Chem. 2020 , 11 , 3546−3550..

Doss, S. S.; Bhatt, N. P.; Jayaraman, G. Improving the accuracy of hyaluronic acid molecular weight estimation by conventional size exclusion chromatography. J. Chromatogr. B 2017 , 1060 , 255−261..

Page, T. F.; Bresler, W. E. End-group analysis and number-average molecular weight determination of some polyalkylene glycols and glycol polyesters using nuclear magnetic resonance spectroscopy. Anal. Chem. 1964 , 36 , 1981−1985..

Chapman, O. L.; King, R. W. Classification of alcohols by nuclear magnetic resonance spectroscopy. J. Am. Chem. Soc. 1964 , 86 , 1256−1258..

Groom, T.; Babiec Jr, J. S.; Van Leuwen, B. G. End group analysis of polyether polyols by nuclear magnetic resonance (NMR) spectroscopy. J. Cell. Plast. 1974 , 10 , 43−46..

Yeager, F. W.; Becker, J. W. Determination of composition and molecular weight of polyester urethanes by high resolution proton magnetic resonance spectrometry. Anal. Chem. 1977 , 49 , 722−724..

Li, X. H.; McCord, E. F.; Baiagern, S.; Fox, P.; Howell, J. L.; Sahoo, S. K.; Rinaldi, P. L. 2D-NMR studies of a model for Krytox® fluoropolymers. Magn. Reson. Chem . 2011 , 49 , 413−424..

Li, L. L.; Twum, E. B.; Li, X. H.; McCord, E. F.; Fox, P. A.; Lyons, D. F.; Rinaldi, P. L. NMR study of the chain end and branching units in poly(vinylidene fluoride- co -tetrafluoroethylene). Macromolecules 2013 , 46 , 7146−7157..

Chen, D. X.; Gao, L. F.; Li, X. H.; Tu, Y. F. Precise molecular weight determination and structure characterization of end-functionalized polymers: an NMR approach via combination of one-dimensional and two-dimensional techniques. Chinese J. Polym. Sci. 2017 , 35 , 681−692..

Xie, H.; Lu, H.; Zhang, Z.; Li, X. H.; Yang, X. M.; Tu, Y. F. Effect of block number and weight fraction on the structure and properties of poly(butylene terephthalate)-block-poly (tetramethylene oxide) multiblock copolymers. Macromolecules 2021 , 54 , 2703−2710..

Tu, Y. Y.; Wan, X. T.; Huan, J.; Zhu, X.; Li, X. H.; Tu, Y. F. The effect of trifluoroacetic acid on molecular weight determination of polyesters: an in situ NMR investigation. Chinese J. Polym. Sci. 2021 , 39 , 1590−1596..

Hou, J.; Pearce, E. Characterization of polymer molecular weight distribution by NMR diffusometry: experimental criteria and findings. Anal. Chem. 2021 , 93 , 7958−7964..

Huan, J.; Li, J.; Lan, Y. J.; Wang, S.; Li, X. H.; Yang, X. M.; Tu, Y. F. Effect of oligo (ethylene glycol) length on properties of poly(oligoethylene glycol terephthalate)s and their cyclic oligomers. Polymer 2022 , 260 , 125369..

Zhou, Z.; Xia, Y.; Moreno, A.; Vasquez, J. K.; Cong, R. Sensitivity-enhanced spin echo nuclear magnetic resonance pulse sequence for quantitative polymer characterizations with a nuclear magnetic resonance cryoprobe. Macromolecules 2023 , 56 , 7125−7131..

Giraudeau, P. Quantitative NMR spectroscopy of complex mixtures. Chem. Commun. 2023 , 59 , 6627−6642..

Li, J.; Wang, S.; Lu, H. J.; Tu, Y. Y.; Wan, X. T.; Li, X. H.; Tu, Y. F.; Li, C. Y.Helical crystals in aliphatic copolyesters: from chiral amplification to me chanical property enhancement. ACS Macro Lett. 2023 , 12 , 369−375..

Li, J.; Wang, S.; Lu, H. J.; Lan, Y. J.; Li, X. H.; Tu, Y. F. Chemical recycling of poly(ethylene furanoate) into value-added poly(ethylene- co -isosorbide furanoate). Chinese J. Polym. Sci. 2023 , 41 , 1533−1542..

Zhang, W. H.; Lan, Y. J.; Lu, C. H.; Sun, Z. Y.; Lu, H. J.; Li, X. H.; Tu, Y. F. Application of nuclear magnetic resonance technology in component analysis of blooming on rubber product surface. Chin. J. Anal. Chem. 2023 , 51 , 405−411..

Pasek-Allen, J. L.; Wilharm, R. K.; Bischof, J. C.; Pierre, V. C. NMR characterization of polyethylene glycol conjugates for nanoparticle functionalization. ACS Omega 2023 , 8 , 4331−4336..

Ruzicka, E.; Pellechia, P.; Benicewicz, B. C. Polymer molecular weights via DOSY NMR. Anal. Chem. 2023 , 95 , 7849−7854..

Yin, T.; Lu, J.; Liu, Q.; Zhu, G.; Zhang, W.; Jiang, Z. Validated quantitative 1 H NMR method for simultaneous quantific ation of indole alkaloids in Uncaria rhynchophylla. ACS Omega 2021 , 6 , 31810−31817..

Moutzouri, P.; Kiraly, P.; Phillips, A. R.; Coombes, S. R.; Nilsson, M.; Morris, G. A. 13 C satellite-free 1 H NMR spectra. Anal. Chem . 2017 , 9 : 11898−11901..

Malz, F.; Jancke, H. Validation of quantitative NMR. J. Pharm. Biomed. Anal. 2005 , 38 , 813−823..

Kuznetsov, D. M.; Tumanov, V. V.; Smit, W. A. Cationic polymerization of styrenes under essentially neutral conditions. J. Polym. Res. 2013 , 20 , 1−6..

Pauli, G. F.; Godecke, T.; Jaki, B. U.; Lankin, D. C. Quantitative 1 H NMR. Development and potential of an analytical method: an update. J. Nat. Prod. 2012 , 75 , 834−851..

Levitt, M. H.; Bodenhausen, G.; Ernst, R. R. The illusions of spin decoupling. J. Magn. Reson. 1983 , 53 , 443−461..

Bahadoor, A.; Brinkmann, A.; Melanson, J. E. 13 C-Satellite decoupling strategies for improving accuracy in quantitative nuclear magnetic resonance. Anal. Chem . 2020 , 93 : 851−858..

Kupče, Ē. Perspectives of adiabatic decoupling in liquids. J. Magn. Reson. 2020 , 318 , 106799..

Xu, S. Y.; Wu, F.; Li, Z. K; Zhu, X., Li, X. H.; Wang, L.; Tu, Y. F. A green cascade polymerization method for the facile synthesis of sustainable poly(butylene- co -decylene terephthalate) copolymers. Polymer 2019 , 178 , 121591..

Al-Aasmi, Z. H.; Shchukina, A.; Butts, C. P. Accelerating quantitative 13 C NMR spectra using an extended acquisition time (EXACT) method. Chem. Commun. 2022 , 58 , 7781−7784..

Wei, R.; Dickson, C. L.; Uhrin, D.; Lloyd-Jones, G. C. Rapid estimation of T 1 for quantitative NMR. J. Org. Chem. 2021 , 86 , 9023−9029..

Kim, S. Y.; Meyer, H. W.; Saalwächter, K.; Zukoski, C. F. Polym er dynamics in PEG-silica nanocomposites: effects of polymer molecular weight, temperature and solvent dilution. Macromolecules 2012 , 45 , 4225−4237..

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