REACTION KINETICS OF HEXAMETHYLENE DIISOCYANATE AND POLYPROPYLENE GLYCOLS

2014 ◽  
Vol 87 (4) ◽  
pp. 617-628
Author(s):  
Min-Tzung Ye ◽  
Shinn-Gwo Hong

ABSTRACT The kinetics of the reaction between hexamethylene diisocyanate (HDI) and polypropylene glycols (PPG) of different molecular weights toward the synthesis of polyurethanes with versatile properties was studied using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). From the dynamic exotherms observed in DSC, it was found that the Kissinger equation modified by an additional temperature term in its frequency factor term was able to accurately describe the isothermal reaction kinetics of all HDI/PPG reactions. The modification can be justified by analyses with the Ozawa method and the modulus observed under DMA measurements. Regardless of the type of PPG used, the frequency factors changed with respect to the degree of conversion and maximized at near 70% conversion. The derivation of the modified kinetic equation is presented. In addition, the empirical equations describing the dependence of the activation energies and frequency factors on the molecular weights of PPG were also derived.

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Ali Kuliaei ◽  
Iraj Amiri Amraei ◽  
Seyed Rasoul Mousavi

Abstract The purpose behind this research was to determine the optimum formulation and investigate the cure kinetics of a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin cured by dicyandiamide and diuron for use in prepregs. First, all formulations were examined by the tensile test, and then, the specimens with higher mechanical properties were further investigated by viscometry and tack tests. The cure kinetics of the best formulation (based on tack test) in nonisothermal mode was investigated using differential scanning calorimetry at different heating rates. Kissinger and Ozawa method was used for determining the kinetic parameters of the curing process. The activation energy obtained by this method was 71.43 kJ/mol. The heating rate had no significant effect on the reaction order and the total reaction order was approximately constant ( m + n ≅ 2.1 $m+n\cong 2.1$ ). By comparing the experimental data and the theoretical data obtained by Kissinger and Ozawa method, a good agreement was seen between them. By increasing the degree of conversion, the viscosity decreased; as the degree of conversion increased, so did the slope of viscosity. The results of the tack test also indicated that the highest tack could be obtained with 25% progress of curing.


1990 ◽  
Vol 10 (3) ◽  
pp. 293-310 ◽  
Author(s):  
Vincent L. Chiang ◽  
Jun Yu ◽  
Robert C. Eckert

2020 ◽  
Vol 4 (3) ◽  
pp. 111
Author(s):  
Zohre Karami ◽  
Seyed Mohammad Reza Paran ◽  
Poornima Vijayan P. ◽  
Mohammad Reza Ganjali ◽  
Maryam Jouyandeh ◽  
...  

Layered double hydroxide (LDH) minerals are promising candidates for developing polymer nanocomposites and the exchange of intercalating anions and metal ions in the LDH structure considerably affects their ultimate properties. Despite the fact that the synthesis of various kinds of LDHs has been the subject of numerous studies, the cure kinetics of LDH-based thermoset polymer composites has rarely been investigated. Herein, binary and ternary structures, including [Mg0.75 Al0.25 (OH)2]0.25+ [(CO32−)0.25/2∙m H2O]0.25−, [Mg0.75 Al0.25 (OH)2]0.25+ [(NO3−)0.25∙m H2O]0.25− and [Mg0.64 Zn0.11 Al0.25 (OH)2]0.25+ [(CO32−)0.25/2∙m H2O]0.25−, have been incorporated into epoxy to study the cure kinetics of the resulting nanocomposites by differential scanning calorimetry (DSC). Both integral and differential isoconversional methods serve to study the non-isothermal curing reactions of epoxy nanocomposites. The effects of carbonate and nitrate ions as intercalating agents on the cure kinetics are also discussed. The activation energy of cure (Eα) was calculated based on the Friedman and Kissinger–Akahira–Sunose (KAS) methods for epoxy/LDH nanocomposites. The order of autocatalytic reaction (m) for the epoxy/Mg-Al-NO3 (0.30 and 0.254 calculated by the Friedman and KAS methods, respectively) was smaller than that of the neat epoxy, which suggested a shift of the curing mechanism from an autocatalytic to noncatalytic reaction. Moreover, a higher frequency factor for the aforementioned nanocomposite suggests that the incorporation of Mg-Al-NO3 in the epoxy composite improved the curability of the epoxy. The results elucidate that the intercalating anions and the metal constituent of LDH significantly govern the cure kinetics of epoxy by the participation of nitrate anions in the epoxide ring-opening reaction.


2014 ◽  
Vol 2014 ◽  
pp. 1-9
Author(s):  
R. K. Koul ◽  
Shivani Suri ◽  
Vishal Singh ◽  
K. K. Bamzai

Synthesis of mixed gadolinium calcium heptamolybdate (GdCaHM) system in silica gel medium using single gel single tube technique has been successfully achieved. The grown crystal exhibits various morphologies, which includes spherulites, multifaceted, and square platelets. The nature of the grown material was established by X-ray diffraction (XRD) studies. Fourier transform infrared spectroscopy (FTIR) study signifies the presence of heptamolybdate (Mo7O24) and water symmetry structure, whereas energy dispersive X-ray analysis (EDAX) establishes the stoichiometric of the grown crystal as GdCaMo7O24·8H2O. The thermal behaviour was studied using the thermoanalytical techniques, which include thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). Results obtained on the application of TG based models, namely, Horowitz-Metzger, Coats-Redfern, and Piloyan-Novikova, suggest the contracting cylindrical model as the relevant model for the thermal decomposition of the material. The kinetic parameters, namely, the order of reaction (n), activation energy (Ea), frequency factor (Z), and entropy (ΔS*), were also calculated using these three models.


2010 ◽  
Vol 160-162 ◽  
pp. 1712-1715
Author(s):  
Guang Heng Wang

The polymerization reaction kinetics of biodegradable polyurethane extended with soy protein isolate (SPI) with dibutyltin dilaurate (DBTDL) as the curing catalyst was studied by means of non-isothermal differential scanning calorimetry (DSC). Model-free methods, Kissinger method and Ozawa method, were applied for analyzing the DSC data. The Ea and lnA obtained from Kissinger method for catalyzed reaction between toluene diisocyanate (TDI) and Polyoxypropyleneglycol (PPG) are 60.80 kJ•mol-1 and 12.09, and for catalyzed reaction among TDI, PPG, and SPI they were 65.91 kJ•mol-1and 14.04. Similarly the Ea obtained from Ozawa method for catalyzed reaction between TDI and PPG and catalyzed reaction among TDI, PPG, and SPI were 63.49 kJ•mol-1 and 64.78 kJ•mol-1, respectively. The results showed that, the incorporation of a small amount of SPI into polyurethane did not affect the reaction kinetic strongly, but increases the reaction activation energy Ea and lnA.


2020 ◽  
Author(s):  
Lyaysan Amirova ◽  
Fabian Schadt ◽  
Markus Grob ◽  
Christian Brauner ◽  
Thomas Ricard ◽  
...  

AbstractA high temperature resistant novolac cyanate ester was blended with polyethersulfone (PES) with different molecular weights using the solvent-free approach. The phase separation, curing behavior and thermal properties were studied using hot stage microscopy, differential scanning calorimetry and dynamic mechanical analysis. Results showed the difference in the morphology for blends with different molecular weight PES explained by possible network formation. The influence of PES content on the glass transition temperature and mechanical properties was investigated. The most significant toughening effect (increase of 132% in fracture toughness) was achieved on a functionalized low molecular weight PES (20 parts per hundred of resin, phr). Rheology investigation allowed to estimate the optimal content of PES (15 phr) for further prepreg manufacturing.


Coatings ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 1266
Author(s):  
Xing Zhang ◽  
Yucun Liu ◽  
Tao Chai ◽  
Zhongliang Ma ◽  
Kanghui Jia

In this research, differential scanning calorimetry (DSC) was employed to compare the curing reaction kinetics of the epoxidized hydroxyl terminated polybutadiene-isophorone diisocyanate (EHTPB-IPDI) and hydroxyl terminated polybutadiene-isophorone diisocyanate (HTPB-IPDI) binder systems. Glass transition temperature (Tg) and mechanical properties of the EHTPB-IPDI and HTPB-IPDI binder systems were determined using the DSC method and a universal testing machine, respectively. For the EHTPB-IPDI binder system, the change of viscosity during the curing process in the presence of dibutyltin silicate (DBTDL) and tin 2-ethylhexanoate (TECH) catalysts was studied, and the activation energy was estimated. The results show that the activation energies (Ea) of the curing reaction of the EHTPB-IPDI and HTPB-IPDI binder systems are 53.8 and 59.1 kJ·mol−1, respectively. While their average initial curing temperatures of the two systems are 178.2 and 189.5 °C, respectively. The EHTPB-IPDI binder system exhibits a higher reactivity. Compared with the HTPB-IPDI binder system, the Tg of the EHTPB-IPDI binder system is increased by 5 °C. Its tensile strength and tear strength are increased by 12% and 17%, respectively, while its elongation at break is reduced by 10%. Epoxy groups and isocyanates react to form oxazolidinones, thereby improving the mechanical properties and thermal stability of polyurethane materials. These differences indicate that the EHTPB-IPDI binder system has better thermal stability and mechanical properties. During the EHTPB-IPDI binder system’s curing process, the DBTDL catalyst may ensure a higher viscosity growth rate, indicating a better catalytic effect, consistent with the prediction results obtained using the non-isothermal kinetic analysis method.


2014 ◽  
Vol 668-669 ◽  
pp. 91-94 ◽  
Author(s):  
Xiao Fang He ◽  
Chang Wen Miao ◽  
Yong Hao Wu ◽  
Xin Xin Cao ◽  
Dan Liu

The thermal reaction kinetics of fly ash cement pastes were studied by Differential Scanning Calorimetry (DSC) and Thermal Gravity Analysis-Differential Thermal Gravity (TG-DTG) method, the kinetics parameters such as apparent activation energy was calculated by the Kissinger method, and the physical parameters were obtained. The result show that the fly ash cement pastes performance three endothermic reaction stages at different heating rates, peak temperatures of each stage at the range of 91.85~121.08°C, 453.93~496.48°C, and 680.21~751.62°C. TG-DTG show there were three thermal decomposition stages, thermal dehydration reaction apparent activation energy of fly ash cement pastes in each stage were 47.23kJ/mol, 128.84kJ/mol, and 134.07kJ/mol.


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