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The preparation of hybrid trimer by cyclo-oligomerization of TDI and HDI and its curing process with polyols to form elastic PU coating

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Abstract

The hybrid cyclic isocyanate trimer with appropriate functionality and good solvent tolerance which can be used as a building block to construct polyurethane (PU) coatings was prepared by cyclo-oligomerization of toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI). Among all the tested catalysts, the self-made catalyst 3-(trimethylammonio)propyl carbonate (Cat. 4) was found to possess enough catalytic efficiency to confirm the NCO conversion to reach about 50% with both high (1 wt%) and low (0.25 wt%) catalyst loading at low temperature (40°C). The IR and NMR results proved the formation of a hybrid trimer, while HPLC results showed hybrid TDI/HDI trimer predominated in the product and only trace amounts of TDI monomer (<0.5 wt%) and oligomer with higher degree of polymerization (DP) remained. Furthermore, the formed hybrid oligomer exhibited excellent solvent tolerance to benzene, chlorinated, and acetate solvents. Consequently, Cat. 4 was demonstrated to be a suitable catalyst for cyclo-oligomerization since it not only possessed enough catalytic efficiency at low temperature but also hardly resulted in higher DP oligomer. Furthermore, the curing process with PTHF-r-PEO polyol was conducted as a pilot experiment to form PU coatings at room temperature. The disappearance of NCO group in IR spectrum as well as higher storage modulus against loss modulus implied the successful curing process. The strain–stress test showed the high tensile strength of formed PU coating, whereas the rheological test and dynamic mechanical analyzer proved the formed PU coating was a typical elastic material with good crosslink structure. These results indicate the promising potential of formed PU made from hybrid TDI/HDI trimer for coating applications.

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Acknowledgments

This work was financially supported by NAO project, BASF Advanced Chemicals Co.

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Authors and Affiliations

  1. School of Materials Science and Engineering, Beijing Institute of Technology, Haidian District, Beijing, 100081, China

    Qian Wang, Lin Ye & Zengguo Feng

  2. Advanced Materials and Systems Research, BASF Advanced Chemicals Co., Ltd, Shanghai, 200137, China

    Hang Xu, ShengZhong Zhou, Sébastien Garnier & Stefan Füldner

Authors
  1. Qian Wang
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  2. Hang Xu
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  3. ShengZhong Zhou
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  4. Sébastien Garnier
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  5. Stefan Füldner
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  7. Zengguo Feng
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Correspondence to Stefan Füldner or Lin Ye.

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Wang, Q., Xu, H., Zhou, S. et al. The preparation of hybrid trimer by cyclo-oligomerization of TDI and HDI and its curing process with polyols to form elastic PU coating. J Coat Technol Res 14, 1279–1288 (2017). https://doi.org/10.1007/s11998-017-9926-5

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