Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2018 Nov 21;10(11):1292.
doi: 10.3390/polym10111292.

Synthesis and Properties of Novel Polyurethanes Containing Long-Segment Fluorinated Chain Extenders

Jia-Wun Li  1 , Hsun-Tsing Lee  2 , Hui-An Tsai  3 , Maw-Cherng Suen  4 , Chih-Wei Chiu  5
Affiliations

Synthesis and Properties of Novel Polyurethanes Containing Long-Segment Fluorinated Chain Extenders

Jia-Wun Li et al. Polymers (Basel). .

Abstract

In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4'-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform ¹H NMR, 19F NMR, 19F⁻19F COSY, ¹H⁻19F COSY, and HMBC analyses on the PFD/PU structures. The results, together with those from Fourier transform infrared spectroscopy (FTIR), verified that the PFD/PUs had been successfully synthesized. Additionally, the soft segment and PFD were changed, after which FTIR and XPS peak-differentiation-imitating analyses were employed to examine the relationship of the hydrogen bonding reaction between the PFD chain extender and PU. Subsequently, atomic force microscopy was used to investigate the changes in the microphase structure between the PFD chain extender and PU, after which the effects of the thermal properties between them were investigated through thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Finally, the effects of the PFD chain extender on the mechanical properties of the PU were investigated through a tensile strength test.

Keywords: chain extender; curve fitting technique; fluorinated polyurethanes; hydrogen bond; nuclear magnetic resonance.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Formula for 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD)/polyurethanes (PUs).
Figure 1
Figure 1
GPC curves of PFD/PUs.
Figure 2
Figure 2
FT-IR spectra of PFD/PUs at wavenumber range of (a) 4000–650 cm−1 and (b) 1900–1000 cm−1.
Figure 3
Figure 3
FT-IR spectra of (a) PFD/PU-01, (b) PFD/PU-02, and (c) PFD/PU-03 at the wavenumber range of 1240–1190 cm–1.
Figure 4
Figure 4
19F NMR spectrum and molecular structure of PFD/PU-03.
Figure 5
Figure 5
19F–19F COSY NMR spectrum of PFD/PU-03.
Figure 6
Figure 6
Structure of the biodegradable fluorine-containing polyurethanes.
Figure 7
Figure 7
1H–19F COSY NMR of PFD/PU-03.
Figure 8
Figure 8
1H–13C HMBC NMR of PFD/PU-03.
Figure 9
Figure 9
XPS survey spectra of PFD/PUs.
Figure 10
Figure 10
O1s fit theory of (a) PFD/PU-01, and (b) PFD/PU-03.
Figure 11
Figure 11
C1s fit theory of PFD/PUs.
Figure 12
Figure 12
Atomic force microscopy (AFM) topographic and phase images of PFD/PUs: (a) PFD/PU-01, (b) PFD/PU-02, and (c) PFD/PU-03.
Figure 13
Figure 13
TGA and DTG curves of PFD/PUs.
Figure 14
Figure 14
DSC thermograms of PFD/PUs.
Figure 15
Figure 15
DMA (a) tan δ and (b) loss modulus (E’’) curves of PFD/PUs.
Figure 16
Figure 16
Tensile properties of PFD/PUs.
See this image and copyright information in PMC

References

    1. Alagi P., Choi Y.J., Hong S.C. Preparation of vegetable oil-based polyols with controlled hydroxyl functionalities for thermoplastic polyurethane. Eur. Polym. J. 2016;78:46–60. doi: 10.1016/j.eurpolymj.2016.03.003. - DOI
    1. Schneider N.S., Sung C.S.P., Matton R.W., Illinger J.L. Thermal Transition Behavior of Polyurethanes Based on Toluene Diisocyanate. Macromolecules. 1975;8:62–67. doi: 10.1021/ma60043a014. - DOI
    1. Paik Sung C.S., Schneider N.S. Structure-property relationships of polyurethanes based on toluene di-isocyanate. J. Mater. Sci. 1978;13:1689–1699. doi: 10.1007/BF00548732. - DOI
    1. Guo Y., Zhang R., Xiao Q., Guo H., Wang Z., Li X., Chen J., Zhu J. Asynchronous fracture of hierarchical microstructures in hard domain of thermoplastic polyurethane elastomer: Effect of chain extender. Polymer. 2018;138:242–254. doi: 10.1016/j.polymer.2018.01.035. - DOI
    1. Oprea S. Effect of Composition and Hard-segment Content on Thermo-mechanical Properties of Cross-linked Polyurethane Copolymers. High Perform. Polym. 2009;21:353–370. doi: 10.1177/0954008308092071. - DOI

LinkOut - more resources