Citation: Dong-xue Chen, Ling-feng Gao, Xiao-hong Li, Ying-feng Tu. Precise Molecular Weight Determination and Structure Characterization of End-functionalized Polymers: An NMR Approach via Combination of One-dimensional and Two-dimensional Techniques[J]. Chinese Journal of Polymer Science, ;2017, 35(5): 681-692. doi: 10.1007/s10118-017-1919-4 shu

Precise Molecular Weight Determination and Structure Characterization of End-functionalized Polymers: An NMR Approach via Combination of One-dimensional and Two-dimensional Techniques

Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

Corresponding author: Xiao-hong Li, lxh83@suda.edu.cn Ying-feng Tu, tuyingfeng@suda.edu.cn
Received Date: 3 November 2016
Revised Date: 29 November 2016
Accepted Date: 29 November 2016

Fund Project: This work was financially supported by the National Natural Science Foundation of China Nos. 21274099, 21305098 and 21474067

We present here the application of one-dimensional and two-dimensional NMR techniques to characterize the structure of methoxyl end-functionalized polystyrenes (PS). The peaks in ¹H-NMR spectra corresponding to main-chain, side-chain and chain-end groups are assigned by ¹H-¹H gCOSY, ¹H-¹³C gHSQC and gHMBC spectra. For the first time, the spin-lattice relaxation time (T₁) of protons of the chain-ends is revealed to be affected more by polymer molecular weight (MW) than by the protons of the main-chains and the side-chains (almost independent from MW). As a result, a much higher delay time (d1) for chain-ends (d1 > 20T₁) is needed for quantitative NMR measurement when using end-group estimation method to obtain the MW of PS, which is in accordance with the value estimated by GPC. An improved method for the polymer MW determination is established, by combination of different NMR techniques to distinguish the peaks, and a large d1 setting to achieve quantitative NMR analysis.
- NMR spectroscopy,
- Molecular weight determination,
- Quantitative NMR analysis,
- 2D NMR
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