NMR Analysis to Identify Biuret Groups in Common Polyureas

Wei-Guang Qiu; Fei-Long Zhang; Xu-Bao Jiang; Xiang-Zheng Kong

doi:10.1007/s10118-018-2130-y

Your Location：

Home >

Browse articles >

NMR Analysis to Identify Biuret Groups in Common Polyureas

ARTICLE | Updated：2021-02-18

- NMR Analysis to Identify Biuret Groups in Common Polyureas
- NMR Analysis to Identify Biuret Groups in Common Polyureas
- Chinese Journal of Polymer Science 2018年36卷第10期页码：1150-1156
- Affiliations：
  
  College of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China
- Author bio：
  
  chm_jiangxb@ujn.edu.cn (X.B.J.)
  xzkong@ujn.edu.cn (X.Z.K.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 21274054, 21304038 and 51473066), Research Foundation of University of Jinan (No. XKY1604) and by Science & Technology Development Plan of Shandong Province (No. 2017GGX202009), China.
- DOI：10.1007/s10118-018-2130-y
  中图分类号：
- 收稿：2018-01-24，
  
  修回：2018-1-24，
  
  录用：2018-2-19，
  
  网络首发：2018-04-12，
  
  纸质出版：2018-10
- Accepted：
Scan QR Code
Citation: Qiu, W. G.; Zhang, F. L.; Jiang, X. B.; Kong, X. Z. NMR Analysis to Identify Biuret Groups in Common Polyureas. Chinese J. Polym. Sci. 2018, 36(10), 1150–1156.

Wei-Guang Qiu, Fei-Long Zhang, Xu-Bao Jiang, et al. NMR Analysis to Identify Biuret Groups in Common Polyureas[J]. Chinese Journal of Polymer Science, 2018, 36(10): 1150-1156.
Citation: Qiu, W. G.; Zhang, F. L.; Jiang, X. B.; Kong, X. Z. NMR Analysis to Identify Biuret Groups in Common Polyureas. Chinese J. Polym. Sci. 2018, 36(10), 1150–1156. DOI： 10.1007/s10118-018-2130-y.

Wei-Guang Qiu, Fei-Long Zhang, Xu-Bao Jiang, et al. NMR Analysis to Identify Biuret Groups in Common Polyureas[J]. Chinese Journal of Polymer Science, 2018, 36(10): 1150-1156. DOI： 10.1007/s10118-018-2130-y.

摘要

Abstract

Polyureas (PU) are well known as a class of high impact engineering materials

and widely used also in emerging advanced applications. As a general observation

most of them are only soluble in a very limited number of highly protonic solvents

which makes their chemical structure analysis a great challenge. Besides the presence of abundant hydrogen bonding

the poor solubility of PU in common organic solvents is often ascribed to the formation of biuret crosslinking in their molecular chains. To clarify the presence of biuret groups in PU has been of great interest. To this end

two samples

based on hexamethylene diisocyanate (HDI) and toluene diisocyanate (TDI) respectively

were synthesized by precipitation polymerization of each of these diisocyanates in water-acetone at 30 °C. Their chemical structures were analyzed by high resolution magic angle spinning (HR-MAS) NMR

and through comparison of their NMR spectra with those of specially prepared biuret-containing polyurea oligomers

it was concluded that biuret group was absent in all the PU prepared at 30 °C. In addition

this NMR analysis was also applied to a PU obtained by copolymerization of TDI with ethylene diamine (EDA) and water at 65 °C in EDA aqueous solution. It was confirmed that biuret unit was also absent in this PU and that EDA was more active than water towards TDI. The presence of EDA was crucial to the formation of uniform PU microspheres. This study provides therefore a reliable method for the analysis of PU chemical structure.

关键词

Keywords

references

Davidson, J. S.; Fisher, J. W.; Hammons, M. I.; Porter, J. R.; Dinan, R. J . Failure mechanisms of polymer-reinforced concrete masonry walls subjected to blast . J. Struct. Eng. , 2005 . 131 ( 8 ): 1194 - 1205 . DOI: 10.1061/(ASCE)0733-9445(2005)131:8(1194) http://doi.org/10.1061/(ASCE)0733-9445(2005)131:8(1194) .

Mohotti, D.; Ngo, T.; Mendis, P.; Raman, S. N . Polyurea coated composite aluminium plates subjected to high velocity projectile impact . Mater. Design , 2013 . 52 ( 24 ): 1 - 16 . .

Samiee, A.; Amirkhizi, A. V.; Nemat-Naser, S . Numerical study of the effect of polyurea on the performance of steel plates under blast loads . Mech. Mater. , 2013 . 64 ( 9 ): 1 - 10 . .

Ley, S. V.; Mitchell, C.; Pears, D.; Ramarao, C.; Yu, J. Q.; Zhou, W . Recyclable polyurea microencapsulated Pd nanoparticles: An efficient catalyst for hydrogenolysis of epoxides . Org. Lett. , 2003 . 5 ( 24 ): 4665 - 4668 . DOI: 10.1021/ol0358509 http://doi.org/10.1021/ol0358509 .

Han, H.; Zhou, Y.; Li, S.; Wang, Y.; Kong, X. Z . Immobilization of lipase from pseudomon as fluorescens on porous polyurea and its application in kinetic resolution of racemic 1-phenylethanol . ACS Appl. Mater. Interfaces , 2016 . 8 ( 39 ): 25714 - 25724 . DOI: 10.1021/acsami.6b07979 http://doi.org/10.1021/acsami.6b07979 .

Jiang, X.; Yu, Y.; Li, X.; Kong, X. Z . High yield preparation of uniform polyurea microspheres through precipitation polymerization and their application as laccase immobilization support . Chem. Eng. J. , 2017 . 328 1043 - 1050 . DOI: 10.1016/j.cej.2017.07.069 http://doi.org/10.1016/j.cej.2017.07.069 .

Jacquemond, M.; Jeckelmann, N.; Ouali, L.; Haefliger, O. P . Perfume-containing polyurea microcapsules with undetectable levels of free isocyanates . J. Appl. Polym. Sci. , 2009 . 114 ( 5 ): 3074 - 3080 . DOI: 10.1002/app.v114:5 http://doi.org/10.1002/app.v114:5 .

Li, J.; Hughes, A. D.; Kalantar, T. H.; Drake, I. J.; Tucker, C. J.; Moore, J. S . Pickering-emulsion-templated encapsulation of a hydrophilic amine and its enhanced stability using poly(allyl amine) . ACS Macro Lett. , 2014 . 3 ( 10 ): 976 - 980 . DOI: 10.1021/mz500455j http://doi.org/10.1021/mz500455j .

Chen, L.; Xu, L.; Shang, H.; Zhang. Z . Microencapsulation of butyl stearate as a phase change material by interfacial polycondensation in a polyurea system . Energ. Convers. Manage. , 2009 . 50 ( 3 ): 723 - 729 . DOI: 10.1016/j.enconman.2008.09.044 http://doi.org/10.1016/j.enconman.2008.09.044 .

Ying, H.; Zhang, Y.; Cheng, J . Dynamic urea bond for the design of reversible and self-healing polymers . Nat. Commun. , 2014 . 5 3218 .

Howarth, G . Polyurethanes, polyurethane dispersions and polyureas: Past, present and future . Surf. Coat. Int. Part B Coat. Trans. , 2003 . 86 ( 2 ): 111 - 118 . DOI: 10.1007/BF02699621 http://doi.org/10.1007/BF02699621 .

Jiang, X.; Li, X.; Zhu, X.; Kong, X. Z . Preparation of highly uniform polyurea microspheres through precipitation polymerization and their characterization . Ind. Eng. Chem. Res. , 2016 . 55 ( 44 ): 11528 - 11535 . DOI: 10.1021/acs.iecr.6b03526 http://doi.org/10.1021/acs.iecr.6b03526 .

Jiang, X.; Kong, X. Z.; Zhu, X . A Novel protocol for the preparation of uniform polymer microspheres with high yields through step polymerization of isophorone diisocyanate . J. Polym. Sci., Part A: Polym. Chem. , 2011 . 49 ( 20 ): 4492 - 4497 . DOI: 10.1002/pola.v49.20 http://doi.org/10.1002/pola.v49.20 .

Sumi, M.; Chokki, Y.; Nakai, Y.; Nakabayashi, M.; Kanzawa, T . Studies on the structure of polyurethane elastomers. I. NMR spectra of the model compounds and some linear polyurethanes . Die Makromol. Chem. , 1964 . 78 ( 1 ): 146 - 156 . DOI: 10.1002/macp.1964.020780112 http://doi.org/10.1002/macp.1964.020780112 .

Chattopadhyay, D. K.; Raju, K. V. S. N . Structural engineering of polyurethane coatings for high performance applications . Prog. Polym. Sci. , 2007 . 32 ( 3 ): 352 - 418 . DOI: 10.1016/j.progpolymsci.2006.05.003 http://doi.org/10.1016/j.progpolymsci.2006.05.003 .

Suzuoki, K.; Kagawa, K.; Fukuma, K.; Uda, B.; Ohmura, J . The analysis of synthetic and side reactions of polyurethaneurea . Nippon Gomu Kyokaishi , 1999 . 72 139 - 143 . DOI: 10.2324/gomu.72.139 http://doi.org/10.2324/gomu.72.139 .

Mathisen, R. J.; Yoo, J. K.; Sung, C. S. P . Dye labeling technique for monitoring the cure of polyimides and polyureas: Model compound studies . Macromolecules , 1987 . 20 ( 6 ): 1414 - 1416 . DOI: 10.1021/ma00172a043 http://doi.org/10.1021/ma00172a043 .

Okuto, H . Studies on the structure of polyurethane elastomers. II. High resolution NMR spectroscopic determination of allophanate and biuret linkages in the cured polyurethane elastomer: Degradation by amine . Die Makromol. Chem. , 1966 . 98 ( 1 ): 148 - 163 . DOI: 10.1002/macp.1966.020980117 http://doi.org/10.1002/macp.1966.020980117 .

Delebecq, E.; Pascault, J.; Boutevin, B.; Ganachaud, F . On the Versatility of urethane/urea bonds: Reversibility, blocked isocyanate, and non-isocyanate polyurethane . Chem. Rev. , 2013 . 113 ( 1 ): 80 - 118 . DOI: 10.1021/cr300195n http://doi.org/10.1021/cr300195n .

Zhang, X.; Zhang, X. Y.; He, Y.; Chen, H . Progress in synthesis and characterization of HDI biuret . Pain Coat. Ind. , 2011 . 41 ( 10 ): 71 - 75 . .

Lapprand, A.; Boisson, F.; Delolme, F.; Méchin, F.; Pascault, J. P . Reactivity of isocyanates with urethanes: conditions for allophanate formation . Polym. Degrad. Stab. , 2005 . 90 ( 2 ): 363 - 373 . DOI: 10.1016/j.polymdegradstab.2005.01.045 http://doi.org/10.1016/j.polymdegradstab.2005.01.045 .

Jiang, X.; Zhu, X.; Arnold, A. A.; Kong, X. Z.; Claverie, J. P . Polyurea structure characterization by HR-MAS NMR spectroscopy . Ind. Eng. Chem. Res. , 2017 . 56 ( 11 ): 2993 - 2998 . DOI: 10.1021/acs.iecr.7b00192 http://doi.org/10.1021/acs.iecr.7b00192 .

Han, H.; Li, S.; Zhu, X.; Jiang, X.; Kong, X. Z . One step preparation of porous polyurea by reaction of toluene diisocyanate with water and its characterization . RSC Adv. , 2014 . 4 ( 63 ): 33520 - 33529 . DOI: 10.1039/C4RA06383J http://doi.org/10.1039/C4RA06383J .

Jiang, X.; Zhu, X.; Kong, X. Z . A facile route to preparation of uniform polymer microspheres by quiescent polymerization with reactor standing still without any stirring . Chem. Eng. J. , 2012 . 213 ( 12 ): 214 - 217 . .

Kong, X. Z.; Jiang, W.; Jiang, X.; Zhu, X . Preparation of core-shell and hollow polyurea microspheres via precipitation polymerization using polyamine as crosslinker monomer . Polym. Chem. , 2013 . 4 ( 24 ): 5776 - 5784 . DOI: 10.1039/c3py00809f http://doi.org/10.1039/c3py00809f .

Li, S. S.; Han, H.; Zhu, X.; Jiang, X.; Kong, X. Z . Preparation and formation mechanism of porous polyurea by reaction of toluene diisocyanate with water and its Application as adsorbent for anionic dye removal . Chinese J. Polym. Sci. , 2015 . 33 ( 8 ): 1196 - 1210 . DOI: 10.1007/s10118-015-1670-7 http://doi.org/10.1007/s10118-015-1670-7 .

Li, S.; Zhu, X.; Kong, X. Z.; Jiang, X . One step synthesis of porous polyurea by using TDI and EDA and its characterization . Acta Polymerica Sinica (in Chinese) , 2016 . ( 3 ): 391 - 398 . .

Yang, Y.; Jiang, X.; Zhu, X.; Kong, X. Z . A facile pathway to polyurea nanofiber fabrication and polymer morphology control in copolymerization of oxydianiline and toluene diisocyanate in acetone . RSC Adv. , 2015 . 5 ( 10 ): 7426 - 7432 . DOI: 10.1039/C4RA15309J http://doi.org/10.1039/C4RA15309J .

Alam, T. M.; Jenkins, J. E. " Advanced Aspects of Spectroscopy”, Intech, Croatia, 2012, p. 279–301.

Li, S.; Zhao, J.; Zhang, Z.; Zhang, J.; Yang, W . Aliphatic thermoplastic polyurethane-ureas and polyureas synthesized through a non-isocyanate route . RSC Adv. , 2015 . 5 ( 9 ): 6843 - 6852 . DOI: 10.1039/C4RA12195C http://doi.org/10.1039/C4RA12195C .

Harris, R. F.; Kinney, J. E.; Savina, M. R.; Jeor, V. L. S.; Bicerano, J.; Durvasula, V. R.; Moreno, L. N . Synthesis and characterization of urea-based polyureas: 1 . Urea-terminated poly(1,6-hexamethyleneurea) polyol dispersions. Polymer , 1995 . 36 ( 22 ): 4275 - 4285 . .

Edwards, P. A.; Striemer, G.; Webster, D. C . Synthesis, characterization and self-crosslinking of glycidyl carbamate functional resins . Prog. Org. Coat. , 2006 . 57 ( 2 ): 128 - 139 . DOI: 10.1016/j.porgcoat.2006.08.002 http://doi.org/10.1016/j.porgcoat.2006.08.002 .

Wendisch, D.; Reiff, H.; Dieterich, D . Kernresonanzspektroskopische beiträge zur struktur und stereochemie von (cyclo)aliphatischen isocyanaten und deren folgeprodukten . Angew. Makromol. Chem. , 1986 . 141 ( 1 ): 173 - 183 . DOI: 10.1002/apmc.1986.051410117 http://doi.org/10.1002/apmc.1986.051410117 .

Zhang, F.; Jiang, X.; Zhu, X.; Chen, Z.; Kong, X. Z . Preparation of uniform and porous polyurea microspheres of large size through interfacial polymerization of toluene diisocyanate in water solution of ethylene diamine . Chem. Eng. J. , 2016 . 303 48 - 55 . DOI: 10.1016/j.cej.2016.05.145 http://doi.org/10.1016/j.cej.2016.05.145 .

Entelis, S. G.; Nesterov, O. V . Kinetics and mechanism of the reactions of isocyanates with compounds containing " active” hydrogen . Russ. Chem. Rev. , 1966 . 35 ( 12 ): 917 - 930 . DOI: 10.1070/RC1966v035n12ABEH001555 http://doi.org/10.1070/RC1966v035n12ABEH001555 .

Lu, X.; Wang, Y.; Wu, X . Molecular interactions in polyurea by 1-D and 2-D NMR . Polymer , 1993 . 34 ( 1 ): 56 - 60 . DOI: 10.1016/0032-3861(93)90283-G http://doi.org/10.1016/0032-3861(93)90283-G .

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Fluorescent Polyurea-Carbon Dots: Preparation, Characterization and Use as Sensor for Doxycycline Detection

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

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

Pyrimidoisoindigo-based Polymers for Ambipolar Charge Transport

Tunable Circularly Polarized Luminescence of Helical Poly(phenylacetylene)s via Side-chain-to-Backbone Förster Resonance Energy Transfer