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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

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Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (1) : 80-89    https://doi.org/10.1007/s11705-018-1763-2
RESEARCH ARTICLE
The influence of the NCO/OH ratio and the 1,6-hexanediol/dimethylol propionic acid molar ratio on the properties of waterborne polyurethane dispersions based on 1,5-pentamethylene diisocyanate
Jiao Feng1, Qiuhao Lu1, Weimin Tan2, Kequan Chen1(), Pingkai Ouyang1
1. State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, China
2. National Engineering Research Center for Coatings, CNOOC Changzhou Paint and Coatings Industry Research Institute Co., Ltd., Changzhou 213016, China
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Abstract

1,5-Pentamethylene diisocyanate, a novel aliphatic diisocyanate formed from bio-based 1,5-pentamethylenediamine, has been used as a hard segmented material to synthesize polyurethane. In this study, several waterborne polyurethane (WPU) dispersions have been successfully prepared by a prepolymer process from 1,5-pentamethylene diisocyanate poly(polyether) with different NCO/OH ratios and 1,6-hexanediol (HDO)/dimethylol propionic acid (DMPA) molar ratios. The Fourier transform infrared (FTIR) spectra, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, and a mechanical tensile test were used to investigate the structures, thermal stability, phase separation, crystallinity, mechanical properties, and adhesive performance of the WPU dispersions. The FTIR results indicate that the degree of hydrogen bonding and the numbers of urea groups increase as the NCO/OH ratio and HDO/DMPA molar ratio increase. Furthermore, the phase separation increases and the thermal stability decreases as the NCO/OH ratio increases or the HDO/DMPA molar ratio decreases. Finally, WPU3.0-2.4 (NCO/OH=3, HDO/DMPA=2.4) exhibits a maximum tensile strength and shear strength, pointing to its possible use as an adhesive. These results could provide a very valuable reference for industrial applications of WPU.
Keywords 1,5-pentamethylene diisocyanate      polyurethane      water based     
Corresponding Author(s): Kequan Chen   
Just Accepted Date: 10 July 2018   Online First Date: 19 December 2018    Issue Date: 25 February 2019
 Cite this article:   
Jiao Feng,Qiuhao Lu,Weimin Tan, et al. The influence of the NCO/OH ratio and the 1,6-hexanediol/dimethylol propionic acid molar ratio on the properties of waterborne polyurethane dispersions based on 1,5-pentamethylene diisocyanate[J]. Front. Chem. Sci. Eng., 2019, 13(1): 80-89.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1763-2
https://academic.hep.com.cn/fcse/EN/Y2019/V13/I1/80
Fig.1  Scheme1 Synthesis route of the WPU dispersions
Samples NCO/OH ratio HDO/DMPA molar ratio N210/g PDI/g DMPA/g HDO/g TEA/g
WPU2.2-1.8 2.2 1.8 34.1 11.5 2.56 4.15 1.93
WPU2.6-1.8 2.6 1.8 28.0 11.5 2.25 3.70 1.69
WPU3.0-1.8 3.0 1.8 25 11.5 2.05 3.31 1.55
WPU3-2.0 3.0 2.0 25 11.5 1.93 3.42 1.45
WPU3-2.2 3.0 2.2 25 11.5 1.81 3.52 1.36
WPU3-2.4 3.0 2.4 25 11.5 1.70 3.62 1.28
Tab.1  Sample designations and compositions of the WPU dispersions
Fig.2  FTIR spectra of (a) polyether, PDI, and prepolymer, (b) WPU films with different NCO/OH ratios, and (c) the carbonyl groups (stretching vibration)
Fig.3  TGA curves of WPU films with different NCO/OH ratios
Samples Residual Soft segments Hard segments T10%/°C T50%/°C Residue at 500°C/wt-%
T/°C Weight loss/wt-% T/°C Weight loss/wt-% T/°C Weight loss/wt-%
WPU2.2-1.8 ? ? 367 30 284, 343 17.2, 51.9 284 340 0.9
WPU2.6-1.8 150 6.8 367 26 285, 340 11.2, 55.3 274 339 0.7
WPU3.0-1.8 179 6.9 370 16.8 281, 342 11, 62.8 267 332 2.5
Tab.2  TGA data of WPU films with different NCO/OH ratio
Fig.4  DSC thermograms of WPU films with different NCO/OH ratios
Fig.5  XRD of WPU films with different NCO/OH ratios
Fig.6  FTIR spectra of (a) WPU films with different HDO/DMPA molar ratio, and (b) C=O stretching vibrations
Fig.7  TGA curves of WPU films with different HDO/DMPA molar ratios
Fig.8  DSC thermograms of WPU films with different HDO/DMPA molar ratios
Samples Residual T10%/°C T50%/°C Tmax/°C Residue at 500°C /wt-% TgSS/°C Tm/°C ΔHm/(J?g−1)
T/°C Weight loss/wt-%
WPU3.0-1.8 179 6.9 267 332 342 2.5 ?47.6 79.3 1.05
WPU3.0-2.0 186 4.3 287 336 342 0.43 ?42.6 73.58 3.83
WPU3.0-2.2 194 4.0 289 340 342 0.46 ?42.0 73.75 4.09
WPU3.0-2.4 196 3.0 294 339 342 0.48 ?41.8 75.19 3.63
Tab.3  TGA data and DSC data of WPU films with different HDO/DMPA molar ratios
Fig.9  XRD of WPU films with different HDO/DMPA molar ratios
Fig.10  Tensile strength, elongation at break, and shear strength of WSPU films with different HDO/DMPA molar ratios
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