The Effect of Trifluoroacetic Acid on Molecular Weight Determination of Polyesters: An <italic style="font-style: italic">in Situ</italic> NMR Investigation

Yan-Yan Tu; Xue-Ting Wan; Jie Huan; Xiang Zhu; Xiao-Hong Li; Ying-Feng Tu

doi:10.1007/s10118-021-2605-0

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The Effect of Trifluoroacetic Acid on Molecular Weight Determination of Polyesters: An in Situ NMR Investigation

ARTICLE | Updated：2021-07-23

- The Effect of Trifluoroacetic Acid on Molecular Weight Determination of Polyesters: An in Situ NMR Investigation
- The Effect of Trifluoroacetic Acid on Molecular Weight Determination of Polyesters: An in Situ NMR Investigation
- Chinese Journal of Polymer Science 2021年39卷第12期页码：1590-1596
- Affiliations：
  
  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 (X.H.L.)
  tuyingfeng@suda.edu.cn (Y.F.T.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 21774090), National Key R&D Program of China (No. 2018YFB1105700), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).
- DOI：10.1007/s10118-021-2605-0
  中图分类号：
- 收稿：2021-03-31，
  
  修回：2021-5-6，
  
  录用：2021-5-11，
  
  网络首发：2021-07-23，
  
  纸质出版：2021-10-18
- Accepted：
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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

Yan-Yan Tu, Xue-Ting Wan, Jie Huan, et al. The Effect of Trifluoroacetic Acid on Molecular Weight Determination of Polyesters: An in Situ NMR Investigation[J]. Chinese Journal of Polymer Science, 2021, 39(12): 1590-1596. DOI: 10.1007/s10118-021-2605-0.
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 DOI： 10.1007/s10118-021-2605-0.

Yan-Yan Tu, Xue-Ting Wan, Jie Huan, et al. The Effect of Trifluoroacetic Acid on Molecular Weight Determination of Polyesters: An in Situ NMR Investigation[J]. Chinese Journal of Polymer Science, 2021, 39(12): 1590-1596. DOI: 10.1007/s10118-021-2605-0. DOI：

摘要

Abstract

Due to the poor solubility of aromatic polyesters in common organic solvents

trifluoroacetic acid is usually used as a co-solvent to increase their solubility for characterizations. However

only few studies have reported the side reactions induced by it. We present he

re the application of

in situ

H-NMR techniques to explore its effect on the hydroxyl end-groups

which are usually used for the molecular weight determination of polyesters by end-group estimation method. Using bis(2-hydroxyethyl) terephthalate (BHET) as model compound

H quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time

via

a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent (1:10

). This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid

revealed by the

H-

C gradient-enhanced heteronuclear multiple bond correlation (gHMBC) spectrum. The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate) (PET) with different degrees of polymerization

and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied. Our results show that if a relative error of 5% is allowed

the NMR measurements must be finished within 1.3 h of solution preparation at 25 °C in the mixture solvent. The results were confirmed in PET sample

while in poly(ethylene adipate)

the obtained esterifaction constant is faster that those in aromatic system. The results can be applied to other polymer systems with alcohol functionalized groups

and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.

关键词

Keywords

references

Scheirs, J.; Long, T. E. in Modern polyesters: chemistry and technology of polyesters and copolyesters . John Wiley and Sons, Chichester, 2003 .

Kalakkunnath, S.; Kalika, D. S. . Dynamic mechanical and dielectric relaxtion characteristics of poly(trimethylene terephthalate) . Polymer , 2006 . 47 7085 - 7094 . DOI: 10.1016/j.polymer.2006.08.005 http://doi.org/10.1016/j.polymer.2006.08.005 .

Lotti, N.; Colonna, M.; Fiorini, M.; Finelli, L.; Berti, C. . Poly(butylene terephthalate) modified with ethoxylated bisphenol S with increased glass transition temperature and improved thermal stability . Polymer , 2011 . 52 904 - 911 . DOI: 10.1016/j.polymer.2011.01.018 http://doi.org/10.1016/j.polymer.2011.01.018 .

Gubbels, E.; Jasinska-Walc, L.; Merino, D. H.; Goossens, H.; Koning, C. . Solid-state modification of poly(butylene terephthalate) with a bio-based fatty acid dimer diol furnishing copolyesters with unique morphologies . Macromolecules , 2013 . 46 3975 - 3984 . DOI: 10.1021/ma400559g http://doi.org/10.1021/ma400559g .

Zhang, W.; Li, J.; Li, H.; Jiang, S.; An, L. . Temperature dependence of deformation behavior of poly(butylene terephthalate) . Polymer , 2018 . 143 309 - 315 . DOI: 10.1016/j.polymer.2018.04.030 http://doi.org/10.1016/j.polymer.2018.04.030 .

Zekriardehani, S.; Joshi, A. S.; Jabarin, S. A.; Gidley, D. W.; Coleman, M. R. . Effect of dimethyl terephthalate and dimethyl isophthalate on the free volume and barrier properties of poly(ethylene terephthalate) (PET): amorphous PET . Macromolecules , 2018 . 51 456 - 467 . DOI: 10.1021/acs.macromol.7b02230 http://doi.org/10.1021/acs.macromol.7b02230 .

Schyns, Z. O. G.; Shaver, M. P. . Mechanical recycling of packaging plastics: a review . Macromol. Rapid Commun. , 2021 . 42 2000415 DOI: 10.1002/marc.202000415 http://doi.org/10.1002/marc.202000415 .

Qiu, J.; Ma, S.; Wang, S.; Tang, Z.; Li, Q.; Tian, A.; Xu, X.; Wang, B.; Lu, N.; Zhu, J. . Upcycling of polyethylene terephthalate to continuously reprocessable vitrimers through reactive extrusion . Macromolecules , 2021 . 54 703 - 712 . DOI: 10.1021/acs.macromol.0c02359 http://doi.org/10.1021/acs.macromol.0c02359 .

Fagnani, D. E.; Tami, J. L.; Copley, G.; Clemons, M. N.; Getzler, Y. D. Y. L.; McNeil, A. J. . 100 th Anniversary of macromolecular science viewpo int: Redefining sustainable polymers . ACS Macro Lett. , 2021 . 10 41 - 53 . DOI: 10.1021/acsmacrolett.0c00789 http://doi.org/10.1021/acsmacrolett.0c00789 .

Li, Y.; Makita, Y.; Zhang, G.; Rui, G.; Li, Z.; Zhong, G.; Miyoshi, T.; Huang, H.; Zhu, L. . Effects of rigid amorphous fraction and lamellar crystal orientation on electrical insulation of poly(ethylene terephthalate) films . Macromolecules , 2020 . 53 - 3977 . .

Chou, C.; Liu, Y.; Zhang, Y.; Hsueh, C.; Yang, F.; Lee, S. . Thermomechanical deformation of polyethylene-terephthalate artifcial muscles . Polymer , 2020 . 210 123013 DOI: 10.1016/j.polymer.2020.123013 http://doi.org/10.1016/j.polymer.2020.123013 .

Narimisa, M.; Onyshchenko, Y.; Morent, R.; De Geyter, N. . Improvement of PET surface modifcation using an atmospheric pressure plasma jet with different shielding gases . Polymer , 2021 . 215 123421 DOI: 10.1016/j.polymer.2021.123421 http://doi.org/10.1016/j.polymer.2021.123421 .

Mori, S. . Size exclusion chromatography of poly(ethylene terephthalate) using hexafluoro-2-propanol as the mobile phase . Anal. Chem. , 1989 . 61 1321 - 1325 . DOI: 10.1021/ac00188a005 http://doi.org/10.1021/ac00188a005 .

Sanches, N. B.; Dias, M. L.; Pacheco, E. B. A. V. . Comparative techniques for molecular weight evaluation of poly(ethylene terephthalate) (PET) . Polym. Test. , 2005 . 24 688 - 693 . DOI: 10.1016/j.polymertesting.2005.05.006 http://doi.org/10.1016/j.polymertesting.2005.05.006 .

Liu, F.; Zhang, J.; Wang, J.; Na, H.; Zhu, J. . Incorporation of 1,4-cyclohexanedicarboxylic acid into poly(butylene terephthalate)- b -poly(tetramethylene glycol) to alter thermal properties without compromising tensile and elastic properties . RSC Adv. , 2015 . 5 94091 - 94098 . DOI: 10.1039/C5RA18389H http://doi.org/10.1039/C5RA18389H .

Tanaka, K.; Oouchi, M.; Hayashi, F.; Maeda, H.; Waki, H. . Structural analysis of the end groups and substructures of commercial poly(ethylene terephthalate) by multiple-WET 1 H/ 13 C NMR . Macromolecules , 2016 . 49 5750 - 5754 . DOI: 10.1021/acs.macromol.6b01105 http://doi.org/10.1021/acs.macromol.6b01105 .

Chen, J.; Chen, D.; Huang, W.; Yang, X.; Li, X.; Tu, Y.; Zhu, X. . A one pot facile synthesis of poly(butylene terephthalate)- block -poly(tetramethylene oxide) alternative multiblock copolymers via PROP method . Polymer , 2016 . 107 29 - 36 . DOI: 10.1016/j.polymer.2016.11.001 http://doi.org/10.1016/j.polymer.2016.11.001 .

Zhu, X.; Gu, J.; Li, X.; Yang, X.; Wang, L.; Li, Y.; Li, H.; Tu, Y. . PROP: an in situ cascade polymerization method for the facile synthesis of polyesters . Polym. Chem. , 2017 . 8 1953 - 1962 . DOI: 10.1039/C7PY00068E http://doi.org/10.1039/C7PY00068E .

Paszkiewicz, S.; Szymczyk, A.; Pawlikowska, D.; Irska, I.; Taraghi, I.; Pilawka, R.; Gu, J.; Li, X.; Tu, Y.; Piesowicz, E. . Synthesis and characterization of poly(ethylene terephthalate- co -1,4-cyclohexanedimethylene terephtlatate)- block -poly(tetramethylene oxide) copolymers . RSC Adv. , 2017 . 7 41745 - 41754 . DOI: 10.1039/C7RA07172H http://doi.org/10.1039/C7RA07172H .

Wang, G.; Jiang, M.; Zhang, Q.; Wang, R.; Liang, Q.; Zhou, G. . New bio-based copolyesters poly(trimethylene 2,5-thiophenedicarboxylate- co -trimethylene terephthalate): synthesis, crystallization behavior, thermal and mechanical properties . Polymer , 2019 . 173 27 - 33 . DOI: 10.1016/j.polymer.2019.04.024 http://doi.org/10.1016/j.polymer.2019.04.024 .

Xie, H.; Lu, H.; Zhang, Z.; Li, X.; Yang, X.; Tu, Y. . 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 . DOI: 10.1021/acs.macromol.0c02793 http://doi.org/10.1021/acs.macromol.0c02793 .

Zhao, Y.; Li, Y.; Xie, D.; Chen, J. . Effect of chain extrender on the compatibility, mechanical and gas barrier properties of poly(butylene adipate- co -terephthalate)/poly(propylene carbonate) bio-composites . J. Appl. Polym. Sci. , 2021 . 138 50487 DOI: 10.1002/app.50487 http://doi.org/10.1002/app.50487 .

Cheng, H. N.; English, A. D. in NMR spectroscopy of polymers in solution and in the solid state . American Chem ical Society, Washington DC, 2002 .

Shit, S. C.; Maiti, S. . Application of NMR spectroscopy in molecular weight determination of polymers . Eur. Polym. J. , 1986 . 22 1001 - 1008 . DOI: 10.1016/0014-3057(86)90082-0 http://doi.org/10.1016/0014-3057(86)90082-0 .

Hariharan, R.; Pinkus, A. . Useful NMR solvent mixture for polyesters: trifluoroacetic acid-d/chloroform-d . Polym. Bull. , 1993 . 30 91 - 95 . DOI: 10.1007/BF00296239 http://doi.org/10.1007/BF00296239 .

Päch, M.; Zehm, D.; Lange, M.; Dambowsky, I.; Weiss, J.; Laschewsky, A. . Universal polymer analysis by 1 H NMR using comp lementary trimethylsilyl end groups . J. Am. Chem. Soc. , 2010 . 132 8757 - 8765 . DOI: 10.1021/ja102096u http://doi.org/10.1021/ja102096u .

Li, X.; McCord, E. F.; Baiagern, S.; Fox, P.; Howell, J. L.; Sahooc, S. K.; Rinaldi, P. L. . 2D-NMR studies of a model for Krytox ® fluoropolymers . Magn. Reson. Chem. , 2011 . 49 413 - 424 . DOI: 10.1002/mrc.2763 http://doi.org/10.1002/mrc.2763 .

Chen, D.; Gao, L.; Li, X.; Tu, Y. . 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 . DOI: 10.1007/s10118-017-1919-4 http://doi.org/10.1007/s10118-017-1919-4 .

Wang, W.; Wu, F.; Lu, H.; Li, X.; Yang, X.; Tu, Y. . A cascade polymerization method for the property modification of poly(butylene terephthalate) by the incorporation of isosorbide . ACS Appl. Polym. Mater. , 2019 . 1 2313 - 2321 . DOI: 10.1021/acsapm.9b00332 http://doi.org/10.1021/acsapm.9b00332 .

Xu, S.; Wu, F.; Li, Z.; Zhu, X.; Li, X.; Wang, L.; Li, Y.; Tu, Y. . A green cascade polymerization method for the facile synthesis of sustainable poly(butylene- co -decylene terephthalate) copolymers . Polymer , 2019 . 178 121591 DOI: 10.1016/j.polymer.2019.121591 http://doi.org/10.1016/j.polymer.2019.121591 .

Li, Z.; Li, Y.; Zhao, Y.; Wang, H.; Zhang, Y.; Song, B.; Li, X.; Lu, S.; Hao, X.; Hla, S.; Tu, Y.; Li, X. . Synthesis of metallopolymers and direct visualization of the single polymer chain . J. Am. Chem. Soc. , 2020 . 142 6196 - 6205 . DOI: 10.1021/jacs.0c00110 http://doi.org/10.1021/jacs.0c00110 .

Li, H.; Xu, S.; Li, J.; Tu, Y.; Li, X.; Tu, Y.; Li, J.; Wang, Y.; Li, Z. . Biodegradable all polyester-based multiblock copolymer elastomers with controlled properties . Polym. Chem. , 2021 . 12 1837 - 1845 . DOI: 10.1039/D1PY00076D http://doi.org/10.1039/D1PY00076D .

Zhao, Y.; Gao, L.; Lu, H.; Li, X.; Tu, Y.; Chang, T. . The non-free draining effect for small cyclics in solution . Polymer , 2021 . 213 123202 DOI: 10.1016/j.polymer.2020.123202 http://doi.org/10.1016/j.polymer.2020.123202 .

Youk, J. H.; Kambour, R. P.; MacKnight, W. J. . Polymerization of ethylene terephthalate cyclic oligomers with antimony trioxide . Macromolecules , 2000 . 33 3594 - 3599 . DOI: 10.1021/ma991838d http://doi.org/10.1021/ma991838d .

Jadhav, A. L.; Malkar, R. S.; Yadav, G. D. . Zn- and Ti-modified hydrotalcites for transesterification of dimethyl terephthalate with ethylene glycol: effect of the metal oxide and catalyst synthesis method . ACS Omega , 2020 . 5 2088 - 2096 . DOI: 10.1021/acsomega.9b02230 http://doi.org/10.1021/acsomega.9b02230 .

Kavanagh, P.; Knipe, A. C.; Watts, W. E. . Kinetic study of the esterification of arylmethanols in trifluoroacetic acid: mechanistic change consequent upon aryl substituent effects . J. Chem. Soc., Chem. Commun. , 1979 . 905 - 906 . .

Gillen, C. J.; Knipe, A. C.; Watts, W. E. . A kinetic study of the mechanism of esterification of 1-arylethanols in trifluoroacetic acid . Tetrahedron Lett. , 1981 . 22 597 - 600 . DOI: 10.1016/S0040-4039(01)90166-2 http://doi.org/10.1016/S0040-4039(01)90166-2 .

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DOI：10.1007/s10118-021-2605-0

摘要

Abstract

关键词

Keywords

references