[논문]Control of Mechanical Properties of Polyurethane Elastomers Synthesized with Aliphatic Diisocyanate Bearing a Symmetric Structure

Kojio, Ken; Nozaki, Shuhei; Takahara, Atsushi; Yamasaki, Satoshi

doi:10.7473/ec.2019.54.4.271

Control of Mechanical Properties of Polyurethane Elastomers Synthesized with Aliphatic Diisocyanate Bearing a Symmetric Structure 원문보기

Elastomers and composites = 엘라스토머 및 콤포지트, v.54 no.4, 2019년, pp.271 - 278

Kojio, Ken (Graduate School of Engineering, Kyushu University) , Nozaki, Shuhei (Graduate School of Engineering, Kyushu University) , Takahara, Atsushi (Graduate School of Engineering, Kyushu University) , Yamasaki, Satoshi (Mitsui Chemicals, Inc.)

Abstract ▼ AI-Helper

Polyurethane elastomers (PUEs) were synthesized using trans-1,4-bis(isocyanatomethyl) cyclohexane (1,4-H6XDI), poly(oxytetramethylene) glycol, 1,4-butanediol (BD), and 1,1,1-trimethylol propane (TMP). To control the molecular aggregation state and mechanical properties of these PUEs, hard segment contents of 20 and 30 wt% and BD/TMP ratios of 10/0 and 8/2 were chosen. Differential scanning calorimetry and small-angle X-ray scattering measurements revealed that the degree of microphase separation increased with an increase in both hard segment content and BD ratio. The Young's modulus and strain at break of the 1,4-H6XDI-based PUE were 6-20 MPa and 5-15, respectively. Incorporation of 20% TMP as a cross-linking agent into BD increased the melting temperature of the hard segment chains, that is, heat resistance, and decreased the Young's modulus. This could be due to the low density of the physical cross-linking network and the dispersion of hard segment chains in the soft segment matrix in the PUE in the presence of 20% TMP.

주제어

표/그림 (10)

그림 Figure 1. Synthetic scheme of PUEs by a prepolymer method.
표 Table 1. Density, Gel Fraction, Degree of Swelling of 1,4-H₆XDI-and MDI-based PUEs
그림 Figure 2. ATR-FT-IR spectra of the HX-30-10/0, HX-30-8/2, HX-20-10/0, and HX-20-8/2.
그림 Figure 3. DSC thermograms of the HX-30-10/0, HX-30-8/2, HX-20-10/0, and HX-20-8/2.
그림 Figure 4. WAXD profiles of the HX-30-10/0, HX-30-8/2, HX-20-10/0, HX-20-8/2, and hard segment models.
그림 Figure 5. (a) SAXS profiles and (b) three-dimensional experimental correlation functions of the HX-30-10/0, HX-30-8/2, HX-20-10/0, and HX-20-8/2.
그림 Figure 6. Temperature dependence of dynamic viscoelastic properties of the HX-30-10/0, HX-30-8/2, HX-20-10/0, and HX-20-8/2.
그림 Figure 7. Stress-strain curves of the HX-30-10/0, HX-30-8/2, HX-20-10/0, and HX-20-8/2.
표 Table 2. Degree of Overall Microphase Separation, Diffuse-microphase Boundary Thickness Parameters for 1,4-H₆XDI-based PUEs
표 Table 3. Mechanical Properties of the 1,4-H₆XDI- and MDI-based PUEs Obtained from Stress-Strain Curves

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제안 방법

ATR-FT-IR measurements were carried out in order to evaluate hydrogen bonding state of the urethane carbonyl groups of hard segment chains and ether oxygen of soft segment chains in the PUEs. Figure 2 shows ATR-FT-IR spectra of (a) 3600~3200 cm^-1and (b) 1800~1600 cm^-1 region for the four 1,4-H₆XDI-based PUEs prepared with various hard segment ratio and BD/TMP ratio.
DSC measurement was performed to investigate glass transition temperature and melting point of the PUEs. The DSC curves were obtained using a DSC (Rigaku DSC 8230, Rigaku Denki Co.
Four 1,4-H₆XDI-based PUEs with two different hard segment contents (20 and 30 wt%) and BD/TMP ratios (10/0 and 8/2) (HX-30-10/0, HX-30-8/2, HX-20-10/0, and HX-20-8/2) were synthesized with PTMG as a soft segment. The hard segment chains in the 1,4-H₆XDI-based PUEs crystallized easily forming strong intermolecular hydrogen bonds due to the symmetry of 1,4-H₆XDI molecule.
Imposed strain and frequency were 0.2% and 10 Hz, respectively Uniaxial tensile tests were carried out using an Instron type tensile tester (RTE-1210, Orientec, Co., LTD.) at 20°C.
In this study, four types of 1,4-H₆XDI-based PUEs were synthesized with various hard segment content and BD/TMP ratio. The relationship between structure and properties of the 1,4-H₆XDI-based PUEs were studied by swelling test, infrared spectroscopy (IR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction and small-angle X-ray scattering (WAXD and SAXS), dynamic viscoelastic property mea- surement and tensile testing.
Figure 1 shows the synthetic scheme of a prepolymer method. The 1,4- H₆XDI-based PUEs with two hard segment contents, 20 and 30 wt%, and two TMP contents, 0 and 20 wt%, were synthesized. The nomenclature denotes the type of diisocyanate, hard segment content, and BD/TMP ratio, for example, HX30-8/2 denotes 1,4-H₆XDI-based PUE with hard segment content of 30 wt%, and BD/TMP = 8/2
The state of hydrogen bond of the hard and soft segments in the 1,4-H₆XDI-based PUEs was evaluated by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT-IR). Spectra were obtained with an FTS-3000 EXCALIBUR (Bruker Japan Co.
Peak positions of HX-30 PUEs were lower than for HX20. To discuss in detail, interdomain spacings were determined by analyzing the threedimensional correlation function. Moreover, diffuse phase boundary thickness of hard and soft segments was determined by analyzing the deviation from Porod’s law.
To investigate the crystal structure of the hard segment chains in the PUEs, WAXD measurements were carried out. Figure 4 shows WAXD profiles for the 1,4-H₆XDI-based PUEs prepared with various hard segment contents and BD/ TMP ratios.
Uniaxial tensile tests were carried out using an Instron type tensile tester (RTE-1210, Orientec, Co., LTD.) at 20°C.

대상 데이터

2 m. For WAXD measurements, a flat panel detector was employed, and the camera length was 63 mm. Scattering patterns were collected for 200~500 ms.
Small-angle X-ray scattering (SAXS) and wide-angle Xray diffraction (WAXD) measurements were conducted for the PUEs at the BL03XU8,9 and BL05XU beamline in the SPring-8 facility in Japan. The photon flux was ~1013 photons/s, and the size of beam at the sample was 150 mm × 150 mm.
The PUEs prepared in this study were synthesized in bulk with PTMG, 1,4-H₆XDI and BD and TMP. Figure 1 shows the synthetic scheme of a prepolymer method.

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