• Elastomers and Composites
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• v.58 no.3
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• pp.121-127
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• 2023

The effect of diisocyanate type on the decomposition temperature of polyurethane (PU) hydrolysis was investigated in a subcritical water medium up to 250℃. PU samples were prepared using different types of diisocyanate: two aromatic diisocyanates (4,4'-methylene diphenyl diisocyanate (MDI) and methyl phenylene diisocyanate (TDI)), one unbranched aliphatic diisocyanate (hexamethylene diisocyanate (HDI)), and two cyclic aliphatic diisocyanates (4,4'-methylene dicyclohexyl diisocyanate (H₁₂MDI) and isophorone diisocyanate (IPDI)). The pressure had no effect on hydrolysis in the range of 70-250 bar. The decomposition temperature of the PU samples increased in the following order: TDI-PU (199℃) < H₁₂MDI ≈ IPDI ≈ HDI (218-220℃) < MDI-PU (237℃). This order of increase in temperature is related to the electron-donating ability of the group to connected to the nitrogen of the urethane unit. When the temperature of the (PU + water) mixture reached the specific decomposition temperature, the PU samples hydrolyzed completely within 5 min into primary amine and 1,4-butanediol. The hydrolysis products from MDI-PU and H₁₂MDI-PU were separated into a liquid phase rich in (BD + water) and a solid low phase rich in amine, whereas the products from TDI-, IPDI-, and HDI-PU existed in a single aqueous phase.

• Elastomers and Composites
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• v.49 no.2
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• pp.117-126
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• 2014

Methylene diisocyanate (MDI) was investigated as a novel interfacial modifier to enhance the performances of poly(methyl methacrylate)-modified starch/styrene-butadiene rubber (PMMA-modified starch/SBR) composites. Owing to the formation urethane linkage on one side and ${\pi}-{\pi}$ adhesion on the other side, MDI acted as an intermediated linkage role in the PMMA-modified starch/SBR interfaces, which was evidenced by the morphological, mechanical, dynamic mechanical and thermal decomposition studies. As a result, the presence of MDI significantly improved the mechanical properties and thermal stability of PMMA-modified starch/SBR composites. In addition, the effect of starch concentration on the various performances of the resulted MDI/PMMA-modified starch/SBR composites, such as morphology, vulcanization characteristics, mechanical properties, toluene swelling behavior, and thermal stability were investigated and discussed in detail. The obtained MDI/PMMA-modified starch/SBR composites exhibited superior mechanical properties to carbon black/SBR (CB/SBR) composites, demonstrating the potential use of the renewable starch as a substitute for CB in the rubber compounds.

• Journal of Adhesion and Interface
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• v.23 no.4
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• pp.137-143
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• 2022

In this study, the polyurethane acrylates (PUA) resin with good adhesive and flexibility for adhesive for shoes and clothing were synthesized using that poly(tetramethylene adiphate glycol) (PTAd), poly(tetramethylene ether glycol) (PTMG) as polyester polyol and polyether polyol respectively, including 4,4'-methylene diphenyl diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,4-butandiol (1,4-BD), 2-hydroxyethyl methacrylate (2-HEMA) and dibutyl amine (DBA). The effect of polyol blend in the polyurethane acrylate on thermal and mechanical properties, adhesion strength and flexural strength were studied. The glass transition temperature (T_g) of PUA was confirmed in range of -70~-40 ℃. In addition, the glass transition temperature (T_g), decomposition temperature (T_d), tensile strength adhesion strength and heat resistance were increased as increasing of PTAd amount while the elongation, water resistance and flexural properties were decreased. The synthesized polyurethane acrylate with 5:5 ratio of PTAd and PTMG indicated the highest adhesion strength and flexural properties.

• Journal of Adhesion and Interface
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• v.18 no.4
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• pp.179-182
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• 2017

Waterborne polyurethanes(WPU) based on castor oil were successfully prepared using polycaprolactone diol(PCL), castor oil(CO) and 4,4'-methylene dicyclohexyl diisocyanate($H_{12}MDI$) as soft segment part, dimethylolbutanoic acid (DMBA) as emulsifier, and trimethylamine(TEA) as neutralizer based on different molecular weight of prepolymer. The various properties such as mechanical strength and surface reforming were evaluated using UTM, contact angle, FE-SEM based on the different molecular weight of polyol. Waterborne polyurethanes based on castor oil could be considered as a promising candidate to be applied the various adhesion fields.

• Journal of the Korean Wood Science and Technology
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• v.42 no.4
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• pp.483-490
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• 2014

The effect of microfibrillated cellulose (MFC) content and coupling agent (polymeric methylene diphenyl diisocyanate, pMDI) on the properties of MFC-reinforced polybutylene succinate (PBS) nanocomposite. With increasing MFC content, tensile strength and elastic modulus were increased. More than 1.5 times in tensile strength of PBS/MFC(70/30) nanocomposite was improved by the addition of pMDI (1 phr), compared to the nanocomposite without pMDI. This trend was being significant in nanocomposite with higher MFC content. Thermal stability of the nanocomposite was increased by the addition of pMDI. These improvements is considered to be due to the improvement of MFC dispersion and interfacial adhesion between MFC and PBS matrix.

• Transactions on Electrical and Electronic Materials
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• v.18 no.4
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• pp.211-216
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• 2017

The dielectric properties of two polyurethanes (PUs) with different hard segments, i.e., aromatic methylene di-p-phenyl diisocyanate (MDI) and aliphatic hexamethylene diisocyanate (HDI), were investigated in the temperature range of -100 to $100^{\circ}C$ and in the frequency range of 1 Hz to 3 kHz. The ${\alpha}$-relaxations induced by the glass transition of the equivalent soft segments in the two PUs occurred at relaxation times of ${\tau}=3.46{\times}10^{-3}s$ for MDI-PU and ${\tau}=3.39{\times}10^{-2}s$ for HDI-PU at $-20^{\circ}C$, in accord with the temperature-frequency superposition principle, resulting in similar shifting factors. However, different I-relaxations were observed for the two PUs. The I-relaxation of MDI-PU occurred due to the mobility of the chain extenders near $80^{\circ}C$ with a slower shifting rate than the ${\alpha}$-relaxation. On the other hand, I-relaxation arising from both the extender and the unconstrained hard segments of HDI-PU occurred at $70{\sim}100^{\circ}C$, indicating complicated dielectric behavior due to partial interaction with the ${\alpha}$-relaxation at high frequencies. Thus, the I-relaxation of HDI-PU did not follow the superposition principle. The dielectric behaviors of the PUs were mainly influenced by their phase transitions, which were affected by the structure and components of the materials.

• Textile Coloration and Finishing
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• v.9 no.5
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• pp.63-74
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• 1997

Polyurethane microcapsules were synthesized by interfacial polymerization in an aqueous poly(ethylene glycol) dispersion with ethylenediamine as chain extender of toluene diisocyanate in perfume oil using poly(vinyl alcohol) as the stabilizing agent. The effect of chemical structure on the average particle size and distributions, morphologies, and thermal properties to design microcapsules for the sustained release system was investigated. It came to be known that polyurethane microcapsules with ethylene diamine as chain extender had a rounder, more permeable and controlled release membranes. And the release test of polyurethane microcapsules with different soft segment content was done to certify the effect of long methylene chain. According to the higher molecular weight of polyether polyol, the release rate of microencapsulated disperse dye molecular was faster.

• Journal of Environmental Science International
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• v.27 no.11
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• pp.1023-1028
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• 2018

Shape memory materials are widely used in high-tech industries. Although shape memory polymers have been developed, they have a disadvantage, only unidirectional resilience. Shape memory polymers with bi-directional recovery resilience have been actively studied. In this study, a bidirectional shape memory polyurethane was synthesized using poly(${\varepsilon}$-caprolactone) diol, methylene dicyclohexyl diisocyanate, and hydroxyethyl acrylate. The first physical curing occurred between hard segments and hydrogen bondings when the solution was dried. The second curing in acrylate groups was performed by UV exposure. A degree of curing was analyzed by infrared spectroscopy. The shape memory properties of 2 step-cured polyurethanes were investigated as a function of UV curing time.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.58-65
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• 1983

The mechanical properties (tensile strength, 100% modulus and hardness) of the urethane elastomers prepared from hydroxyl terminated polybutadiene (HTPB), several low molecular weight diols (ethylene glycol, 1, 3-propane diol, 1,4-butane diol, 1,5-pentane diol and 1,6-hexane diol) and two kinds of diisocyanates(TDI: toluene diisocyanate, IPDI: isophorone diisomechanical properties were enhanced for the increases of the concentrations of the urethane group, as predicted. In case of TDI, when the mechanical properties of the elastomers were plotted patterns were observed, which can be explained by hydrogen bondings depending on the number of the methylene carbons. But the mechanical properties of the elastomers derived from IPDI had decreasing curves against the number of methylene carbons in low molecular weight diols, without the characteristic zigzag patterns.

• Elastomers and Composites
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• v.52 no.4
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• pp.266-271
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• 2017

This study describes the influence of the amount of curing agent and curing temperature on the kinetics of polyurethane elastomers. The urethane prepolymer series was prepared by reacting toluene diisocyanate with polytetramethylene ether glycol at $80^{\circ}C$ for 1 h, and 4,4'-methylene bis(2-chloroaniline) was used as the curing agent. The ratio of the amine group of the curing agent to the isocyanate group of the urethane prepolymer was controlled from 0.85 to 1.05 at curing temperatures ranging from 80 to $120^{\circ}C$. The curing rate of the urethane prepolymer was monitored by observing the change in heat flow during the curing process using differential scanning calorimetry (DSC). As either the content of curing agent or the curing temperature was higher, the conversion rate to the polyurethane elastomer was high. The DSC results were compared with those obtained from using real-time FT-IR.